Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

Synthesis and Characterization of ZIF-7 Membranes by In Situ Method.

Zeolitic imidazolate frameworks (ZIFs) have been the focus of interest in adsorption, catalysis, and membrane applications due to their superior thermal and chemical stability, tunable microporous channels, and tailorable physical/chemical properties. In this study, ZIF-7 membranes were successfully prepared on macroporous a-alumina substrate by in situ solvothermal method, without the necessity of seeding or surface modification step. Addition of sodium formate during the reaction facilitates continuous well-intergrown crystalline ZIF-7 layer. As-synthesized ZIF-7 membrane was characterized by XRD, FE-SEM and gas permeation test. The H2 permeance through 5 µm ZIF-7 membrane was 1.9 x 10(-7) mol/m2 x s x Pa with ideal selectivity of H2/CO2 = 15.2.

Mechanisms of enhanced sulfur tolerance on samarium (Sm)-doped cerium oxide (CeO2) from first principles.

The role of samarium (Sm) 4f states and Sm-perturbed O 2p states in determining the sulfur tolerance of Sm-doped CeO2 was elucidated by using the density functional theory (DFT) + U calculation. We find that the sulfur tolerance of Sm-doped CeO2 is closely related to the modification of O 2p states by the strong interaction between Sm 4f and O 2p states. In particular, the availability of unoccupied O 2p states near the Fermi level is responsible for enhancing the sulfur tolerance of Sm-doped CeO2 compared to the pure CeO2 by increasing the activity of the surface lattice oxygen toward sulfur adsorption, by weakening the interaction between Sm-O, and by increasing the migration tendency of the subsurface oxygen ion toward the surface.

Clinical application of a new hemostatic material using mussel-inspired catecholamine hemostat: A pilot study.

BACKGROUNDS/AIMS: This study aimed to evaluate clinical application of InnoSEAL Plus (a mussel-inspired catecholamine hemostat) as a new hemostatic material for humans. METHODS: Patients treated with topical hemostatic patches after liver resection were enrolled. They were divided into an experimental group (InnoSEAL Plus group) and two control groups (TachoSil® group and Surgicel Fibrillar® group) for efficacy evaluation. RESULTS: A total of 15 patients were enrolled. Each group had five patients. The 3-minute hemostasis success rate was 80.0% (4/5 patients) in the InnoSEAL Plus group, 80.0% (4/5 patients) in the TachoSil® group, and 40.0% (2/5 patients) in the Surgicel Fibrillar® group, showing no significant difference in the success rate among these groups (p > 0.05). All three groups exhibited 100% success rate for 10-minute hemostasis. Both InnoSEAL Plus and TachoSil® groups had one patient developing adverse events, which were treated easily with drug administrations. CONCLUSIONS: InnoSEAL Plus is expected to be functionally not inferior to other conventional hemostatic agents. However, it is necessary to confirm this through multicenter prospective studies in the future.

Experimental and Numerical Study of Pd/Ta and PdCu/Ta Composites for Thermocatalytic Hydrogen Permeation.

The development of stable and durable hydrogen (H2) separation technology is essential for the effective use of H2 energy. Thus, the use of H2 permeable membranes, made of palladium (Pd), has been extensively studied in the literature. However, Pd has considerable constraints in large-scale applications due to disadvantages such as very high cost and H2 embrittlement. To address these shortcomings, copper (Cu) and Pd were deposited on Ta to fabricate a composite H2 permeable membrane. To this end, first, Pd was deposited on a tantalum (Ta) support disk, yielding 7.4 × 10-8 molH2 m-1 s-1 Pa-0.5 of permeability. Second, a Cu-Pd alloy on a Ta support was synthesized via stepwise electroless plating and plasma sputtering to improve the durability of the membrane. The use of Cu is cost-effective compared with Pd, and the appropriate composition of the PdCu alloy is advantageous for long-term H2 permeation. Despite the lower H2 permeation of the PdCu/Ta membrane (than the Pd/Ta membrane), about two-fold temporal stability is achieved using the PdCu/Ta composite. The degradation process of the Ta support-based H2 permeable membrane is examined by SEM. Moreover, thermocatalytic H2 dissociation mechanisms on Pd and PdCu were investigated and are discussed numerically via a density functional theory study.

Controlled Coprecipitation of Amorphous Cerium-Based Carbonates with Suitable Morphology as Precursors of Ceramic Electrolytes for IT-SOFCs.

To be suitable as electrolytes in intermediate temperature solid oxide fuel cell (IT-SOFC), ceramic precursors have to be characterized by high sintering aptitude for producing fully densified products which are needed for this kind of application. Therefore, synthesis processes able to prepare highly reactive powders with low costs are noteworthy to be highlighted. It has been shown that amorphous coprecipitates based on cerium doped (and codoped) hydrated hydroxycarbonates can lead to synthesized ceramics with such desired characteristics. These materials can be prepared by adopting a simple coprecipitation technique using ammonium carbonate as precipitating agent. As a function of both the molar ratio between carbonate anions and total metallic cations, and the adopted mixing speed, the coprecipitate can be either amorphous, owning a very good morphology, or crystalline, owning worse morphology, packing aptitude, and sinterability. The amorphous powders, upon a mild calcination step, gave rise to the formation of stable solid solutions of fluorite-structured ceria maintaining the same morphology of the starting powders. Such calcined powders are excellent precursors for sintering ceramic electrolytes at low temperatures and with very high electrical conductivity in the intermediate temperature range (i.e., 500⁻700 °C). Therefore, irrespective of the actual composition of ceria-based systems, by providing an accurate control of both chemical conditions and physical parameters, the coprecipitation in the presence of ammonium carbonate can be considered as one of the most promising synthesis route in terms of cost/effectiveness to prepare excellent ceramic precursors for the next generation of IT-SOFC solid electrolytes.

Enhanced Selectivity to H2 Formation in Decomposition of HCOOH on the Ag19@Pd60 Core-Shell Nanocluster from First-Principles.

In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition.

Hybrid Electrodes of Carbon Nanotube and Reduced Graphene Oxide for Energy Storage Applications.

The choice of electrode materials in lithium ion batteries and supercapacitors is important for the stability, capacity, and cycle life of the device. Despite its low capacity, graphite has often been used as an electrode material due to its inherent stability. Due to an increasing demand for large-capacity energy storage systems, there is also a demand for the development of large-capacity Li ion batteries and supercapacitors. Therefore, carbonaceous materials like graphene and carbon nanotubes (CNTs), which have high stability as well as excellent electrical conductivity and mechanical strength, are receiving attention as new electrode materials. Recently, starting from simply applying graphene and CNTs as electrode materials and progressing to the development of hybrid materials, there have been increasing research efforts in enhancing the performance of Li ion batteries and supercapacitors through the use of carbonaceous materials. This paper will discuss new composite materials and electrode structures that use graphene and CNTs for applications in Li ion batteries and supercapacitors.

Interface modification in solar cell contact electrode using pre-cleaning treatment chemistries.

Promoting and employing photovoltaic power as an alternative energy source, the solar cell industry has made rapid strides. However, improving the efficiency of these solar cells using low-cost fabrication processes is still needed. The interface between the Si surface and the electrode plays a very important role in the process of electrode formation of the solar cell. In this study, the electrode interface underwent four different pre-treatments in order to enhance the efficiency of Si-based solar cells. We analyzed the adhesion properties at the interface between the Si wafer and the electrode and conducted an analysis of the variation in contact resistance between the two contact surfaces. To reduce the cost of the entire experiment, we replaced the existing Ag screen printing-based electrode fabrication method with a low-temperature, low-cost Ni/Cu electroless plating method. The test cells exhibited improved adhesion and therefore improved efficiency as compared to cells treated with the currently used diluted HF.