Recent Advances in Electrocatalysts for Proton Exchange Membrane Fuel Cells and Alkaline Membrane Fuel Cells.

The rapid progress of proton exchange membrane fuel cells (PEMFCs) and alkaline exchange membrane fuel cells (AMFCs) has boosted the hydrogen economy concept via diverse energy applications in the past decades. For a holistic understanding of the development status of PEMFCs and AMFCs, recent advancements in electrocatalyst design and catalyst layer optimization, along with cell performance in terms of activity and durability in PEMFCs and AMFCs, are summarized here. The activity, stability, and fuel cell performance of different types of electrocatalysts for both oxygen reduction reaction and hydrogen oxidation reaction are discussed and compared. Research directions on the further development of active, stable, and low-cost electrocatalysts to meet the ultimate commercialization of PEMFCs and AMFCs are also discussed.

Hydrogen production from water electrolysis: role of catalysts.

As a promising substitute for fossil fuels, hydrogen has emerged as a clean and renewable energy. A key challenge is the efficient production of hydrogen to meet the commercial-scale demand of hydrogen. Water splitting electrolysis is a promising pathway to achieve the efficient hydrogen production in terms of energy conversion and storage in which catalysis or electrocatalysis plays a critical role. The development of active, stable, and low-cost catalysts or electrocatalysts is an essential prerequisite for achieving the desired electrocatalytic hydrogen production from water splitting for practical use, which constitutes the central focus of this review. It will start with an introduction of the water splitting performance evaluation of various electrocatalysts in terms of activity, stability, and efficiency. This will be followed by outlining current knowledge on the two half-cell reactions, hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), in terms of reaction mechanisms in alkaline and acidic media. Recent advances in the design and preparation of nanostructured noble-metal and non-noble metal-based electrocatalysts will be discussed. New strategies and insights in exploring the synergistic structure, morphology, composition, and active sites of the nanostructured electrocatalysts for increasing the electrocatalytic activity and stability in HER and OER will be highlighted. Finally, future challenges and perspectives in the design of active and robust electrocatalysts for HER and OER towards efficient production of hydrogen from water splitting electrolysis will also be outlined.

Evolution of Active Sites in Pt-Based Nanoalloy Catalysts for the Oxidation of Carbonaceous Species by Combined in Situ Infrared Spectroscopy and Total X-ray Scattering.

We present results from combined in situ infrared spectroscopy and total X-ray scattering studies on the evolution of catalytically active sites in exemplary binary and ternary Pt-based nanoalloys during a sequence of CO oxidation-reactivation-CO oxidation reactions. We find that when within a particular compositional range, the fresh nanoalloys may exhibit high catalytic activity for low-temperature CO oxidation. Using surface-specific atomic pair distribution functions (PDFs) extracted from the in situ total X-ray scattering data, we find that, regardless of their chemical composition and initial catalytic activity, the fresh nanoalloys suffer a significant surface structural disorder during CO oxidation. Upon reactivation in oxygen atmosphere, the surface of used nanoalloy catalysts both partially oxidizes and orders. Remarkably, it largely retains its structural state when the nanoalloys are reused as CO oxidation catalysts. The seemingly inverse structural changes of studied nanoalloy catalysts occurring under CO oxidation and reactivation conditions affect the active sites on their surface significantly. In particular, through different mechanisms, both appear to reduce the CO binding strength to the nanoalloy's surface and thus increase the catalytic stability of the nanoalloys. The findings provide clues for further optimization of nanoalloy catalysts for the oxidation of carbonaceous species through optimizing their composition, activation, and reactivation. Besides, the findings demonstrate the usefulness of combined in situ infrared spectroscopy and total X-ray scattering coupled to surface-specific atomic PDF analysis to the ongoing effort to produce advanced catalysts for environmentally and technologically important applications.

Composition Tunability and (111)-Dominant Facets of Ultrathin Platinum-Gold Alloy Nanowires toward Enhanced Electrocatalysis.

The ability for tuning not only the composition but also the type of surface facets of alloyed nanomaterials is important for the design of catalysts with enhanced activity and stability through optimizing both ensemble and ligand effects. Herein we report the first example of ultrathin platinum-gold alloy nanowires (PtAu NWs) featuring composition-tunable and (111) facet-dominant surface characteristics, and the electrocatalytic enhancement for the oxygen reduction reaction (ORR). PtAu NWs of different bimetallic compositions synthesized by a single-phase and surfactant-free method are shown to display an alloyed, parallel-bundled structure in which the individual nanowires exhibit Boerdijk-Coxeter helix type morphology predominant in (111) facets. Results have revealed intriguing catalytic correlation with the binary composition, exhibiting an activity maximum at a Pt:Au ratio of ∼3:1. As revealed by high-energy synchrotron X-ray diffraction and atomic pair distribution function analysis, NWs of this ratio exhibit a clear shrinkage in interatomic bonding distances. In comparison with PtAu nanoparticles of a similar composition and degree of shrinking of atomic-pair distances, the PtAu NWs display a remarkably higher electrocatalytic activity and stability. The outperformance of NWs over nanoparticles is attributed to the predominant (111)-type facets on the surface balancing the contribution of ensemble and ligand effects, in addition to the composition synergy due to optimal adsorption energies for molecular and atomic oxygen species on the surface as supported by DFT computation of models of the catalysts. The findings open up a new pathway to the design and engineering of alloy nanocatalysts with enhanced activity and durability.

Composition- and Structure-Tunable Gold-Cobalt Nanoparticles and Electrocatalytic Synergy for Oxygen Evolution Reaction.

The increasing energy crisis constitutes an inspiring drive seeking alternative energies such as hydrogen from water splitting which is clean and abundant, but a key challenge for water splitting is the need of highly efficient catalysts for oxygen evolution reaction (OER). This report describes findings of an investigation of the synthesis of gold-cobalt (AuCo) nanoparticles by a facile one-pot and injection method and their use as highly efficient catalysts for OER. While particle size depends on the synthesis method, the composition of the nanoparticles is controlled by feeding ratio of Au and Co precursors in the synthesis. Depending on Co content, the nanoparticles exhibit largely phase-segregated domains with a core (Au)-shell (Co) type of structure at a high level of Co. Upon the thermochemical treatment of carbon-supported AuCo nanoparticles, the redox activity of Co species in the nanoparticles with cycle number is shown to decrease which changes the surface oxidation state of Co species without changing the composition significantly. The electrocatalytic activity for OER in alkaline electrolytes is shown to depend on the bimetallic composition, displaying a maximum activity for an Au:Co ratio of ∼2:3. This dependence is also shown to correlate with the surface oxidation state and redox activities, providing an insight into the electrocatalytic activity. Mechanistic aspects of the electrocataltytic properties are discussed in terms of the bifunctional synergy of Co and Au in the nanoparticle catalysts.

Au-ZnO hybrid nanoflowers, nanomultipods and nanopyramids: one-pot reaction synthesis and photocatalytic properties.

The preparation of noble metal-semiconductor hybrid nanocrystals with controlled morphologies has received intensive interest in recent years. In this study, facile one-pot reactions have been developed for the synthesis of Au-ZnO hybrid nanocrystals with different interesting morphologies, including petal-like and urchin-like nanoflowers, nanomultipods and nanopyramids. In the synthesis strategy, oleylamine-containing solution serves as the reaction medium, and the in situ generated Au seeds play an important role in the subsequently induced growth of ZnO nanocrystals. With the aid of several surfactants, hybrid nanocrystals with different morphologies that have considerable influences on their optical and photocatalytic activities are readily achieved. Through high-resolution transmission electron microscopy measurements, an observed common orientation relationship between ZnO and Au is that ZnO nanocrystals prefer to grow with their polar {001} facets on the {111} facets of Au nanocrystals, and well-defined interfaces are evident. Surface plasmon resonance bands of Au with different positions are observed in the UV-vis spectra, and the UV and visible emissions of ZnO are found to be dramatically reduced. Finally, the as-prepared Au-ZnO nanocrystals exhibit excellent photocatalytic activity for the photodegradation of rhodamine B compared with pure ZnO nanocrystals. The Au-ZnO hybrid nanopyramids show the highest catalytic efficiency, which is correlated with the exposed crystal facets, crystallinity and the formation of hybrid nanostructures. The as-prepared Au-ZnO hybrid nanocrystals are expected to find diverse potential applications in the fields such as photocatalysis, solar energy conversion, sensing and biological detection.

Facile preparation of well-dispersed CeO2-ZnO composite hollow microspheres with enhanced catalytic activity for CO oxidation.

In this article, well-dispersed CeO2-ZnO composite hollow microspheres have been fabricated through a simple chemical reaction followed by annealing treatment. Amorphous zinc-cerium citrate hollow microspheres were first synthesized by dispersing zinc citrate hollow microspheres into cerium nitrate solution and then aging at room temperature for 1 h. By calcining the as-produced zinc-cerium citrate hollow microspheres at 500 °C for 2 h, CeO2-ZnO composite hollow microspheres with homogeneous composition distribution could be harvested for the first time. The resulting CeO2-ZnO composite hollow microspheres exhibit enhanced activity for CO oxidation compared with CeO2 and ZnO, which is due to well-dispersed small CeO2 particles on the surface of ZnO hollow microspheres and strong interaction between CeO2 and ZnO. Moreover, when Au nanoparticles are deposited on the surface of the CeO2-ZnO composite hollow microspheres, the full CO conversion temperature of the as-produced 1.0 wt % Au-CeO2-ZnO composites reduces from 300 to 60 °C in comparison with CeO2-ZnO composites. The significantly improved catalytic activity may be ascribed to the strong synergistic interplay between Au nanoparticles and CeO2-ZnO composites.

Shape-related optical and catalytic properties of wurtzite-type CoO nanoplates and nanorods.

In this paper, we report the anisotropic optical and catalytic properties of wurtzite-type hexagonal CoO (h-CoO) nanocrystals, an unusual nanosized indirect semiconductor material. h-CoO nanoplates and nanorods with a divided morphology have been synthesized via facile solution methods. The employment of flash-heating and surfactant tri-n-octylphosphine favors the formation of plate-like morphology, whereas the utilization of cobalt stearate as a precursor is critical for the synthesis of nanorods. Structural analyses indicate that the basal plane of the nanoplates is (001) face and the growth direction of the nanorods is along the c axis. Moreover, the UV­vis absorption spectra, the corresponding energy gap and the catalytic properties are found to vary with the crystal shape and the dimensions of the as-prepared h-CoO nanocrystals. Furthermore, remarkable catalytic activities for H2 generation from the hydrolysis of alkaline NaBH4 solutions have been observed for the as-prepared h-CoO nanocrystals. The calculated Arrhenius activation energies show a decreasing trend with increasing extension degree along the <001> direction, which is in agreement with the variation of the charge-transfer energy gap. Finally the maximum hydrogen generation rate of the h-CoO nanoplates exceeds most of the reported values of transition metal or noble metal containing catalysts performing in the same reaction system, which makes them a low-cost alternative to commonly used noble metal catalysts in H2 generation from the hydrolysis of borohydrides, and might find potential applications in the field of green energy.

Injection synthesis of Ni-Cu@Au-Cu nanowires with tunable magnetic and plasmonic properties.

A facile nonaqueous injection method has been developed for the construction of one-dimensional nanostructure consisting of a magnetic alloy (Ni-Cu) core and a plasmonic alloy (Au-Cu) shell. The obtained Ni-Cu@Au-Cu nanowires exhibit tunable optical and magnetic properties.