In Situ Engineering of Pd Nanosponge Armored with Graphene Dots Using Br- toward High-Performance and Stable Electrocatalyst for the Hydrogen Evolution Reaction.

In this study, we report a facile synthetic pathway to three-dimensional (3D) Pd nanosponge-shaped networks wrapped by graphene dots (Pd@G-NSs), which show superior electrocatalytic activity toward the hydrogen evolution reaction (HER) and exhibited excellent long-term stability in acidic media. Pd@G-NSs were synthesized by simply mixing Pd precursors, reducing agent, carbon dots (Cdots), and Br- ion at 30 °C. Experimental results and density functional theory (DFT) calculations suggested that the Br- ions played an essential role in accelerating the exfoliation of Cdot, supplying graphene layers, which could wrap the nanosponge-shaped Pd and finally form Pd@G-NS. In the absence of the Br- ions, only aggregated Pd nanoparticles (NPs) were formed and randomly mixed with Cdots. The resultant Pd@G-NS exhibited a high electrochemically active surface area and accelerated charge transport characteristics, leading to its superior electrocatalytic activity toward the HER in acidic media. The HER overpotential of Pd@G-NS was 32 mV at 10 mA cm-2, and the Tafel slope was 33 mV dec-1. Furthermore, the unique Pd@G-NS catalyst showed long-term stability for over 3000 cycles in acidic media as well, owing to the protection of Pd nanosponges by graphene dot wrapping. The overall HER performance of the Pd@G-NS catalyst exceeded that of commercial Pt/C.

Efficient Sn Recovery from SnO2 by Alkane (CxHy=2x+2, 0 ≤ x ≤ 4) Reduction.

We study the mechanism of alkane reduction of SnO2 for efficient low-temperature recovery of Sn from SnO2. Based on thermodynamic simulation results, we comparatively analyze the reduction behavior and the efficiency of SnO2 reduction by H2 and alkanes (CxHy=2x+2, 0 ≤ x ≤ 4). We found that alkanes (n·CxHy) with the higher nx generally complete the reduction of SnO2 (T100) at the lower temperature. Moreover, the T100 of the SnO2 reduction by alkanes (n·CxHy) was decreased from the T100 of pure hydrogen with the same amount of hydrogen atoms (n·Hy). We found that the concentration of a gas phase product mixture, the amount of the produced solid carbon, and the T100 complementary vary as a function of the nx and ny, the total amount of carbon and hydrogen atoms in the reducing gas phase molecules. Our results demonstrate a viability of the low temperature reduction method of SnO2 by alkanes for efficient recovery of Sn from SnO2, which can be applied for Sn recovery from Sn containing industrial wastes or Sn ores with economic value added that is held by the co-produced H2.

Compositional effect of two-dimensional monodisperse AuPd bimetallic nanoparticle arrays fabricated by block copolymer nanopatterning on catalytic activity of CO oxidation.

We present a straightforward approach for fabricating AuPd nanocatalysts based on self-assembled block copolymer nanopatterning. CO oxidation was carried out on AuPd alloy nanoparticles and the activity increased with increasing Pd content; this synergistic activity can be precisely tuned by varying the chemical composition. Theoretical calculations suggest that Pd clusters are required to bind and dissociate O2 for oxidation of coadsorbed CO molecules. Our results suggest that the geometric configuration of the Pd atoms on the surface are a key factor in the catalytic activity.

Design of Reduction Process of SnO2 by CH4 for Efficient Sn Recovery.

We design a novel method for the CH4 reduction of SnO2 for the efficient recovery of Sn from SnO2 through a study combining theory and experiment. The atomic-level process of CH4-SnO2 interaction and temperature-dependent reduction behavior of SnO2 were studied with a combination of a multi-scale computational method of thermodynamic simulations and density functional theory (DFT) calculations. We found that CH4 was a highly efficient and a versatile reducing agent, as the total reducing power of CH4 originates from the carbon and hydrogen of CH4, which sequentially reduce SnO2. Moreover, as a result of the CH4 reduction of SnO2, a mixture of CO and H2 was produced as a gas-phase product (syngas). The relative molar ratio of the produced gas-phase product was controllable by the reduction temperature and the amount of supplied CH4. The laboratory-scale experimental study confirmed that CH4 actively reduces SnO2, producing 99.34% high-purity Sn and H2 and CO. Our results present a novel method for an efficient, green, and economical recycling strategy for Sn with economic value added that is held by the co-produced clean energy source (syngas).

Understanding the atomic-level process of CO-adsorption-driven surface segregation of Pd in (AuPd)147 bimetallic nanoparticles.

When the elements that compose bimetallic catalysts interact asymmetrically with reaction feedstock, the surface concentration of the bimetallic catalysts and the morphology of the reaction center evolve dynamically as a function of environmental factors such as the partial pressure of the triggering molecule. Relevant experimental and theoretical findings of the dynamic structural evolution of bimetallic catalysts under the reaction conditions are emerging, thus enabling the design of more consistent, reliable, and efficient bimetallic catalysts. In an initial attempt to provide an atomic-level understanding of the adsorption-induced structural evolution of bimetallic nanoparticles (NPs) under CO oxidation conditions, we used density functional theory to study the details of CO-adsorption-driven Pd surface segregation in (AuPd)147 bimetallic NPs. The strong CO affinity of Pd provides a driving force for Pd surface segregation. We found that the vertex site of the NP becomes a gateway for the initial Pd-Au swapping and the subsequent formation of an internal vacancy. This self-generated internal vacancy easily diffuses inside the NP and activates Pd-Au swapping pathways in the (100) NP facet. Our results reveal how the surface and internal concentrations of bimetallic NPs respond immediately to changes in the reaction conditions. Our findings should aid in the rational design of highly active and versatile bimetallic catalysts by considering the environmental factors that systematically affect the structure of bimetallic catalysts under the reaction conditions.

Interface engineering for a rational design of poison-free bimetallic CO oxidation catalysts.

We use density functional theory calculations of Pt@Cu core@shell nanoparticles (NPs) to design bifunctional poison-free CO oxidation catalysts. By calculating the adsorption chemistry under CO oxidation conditions, we find that the Pt@Cu NPs will be active for CO oxidation with resistance to CO-poisoning. The CO oxidation pathway at the Pt-Cu interface is determined on the Pt NP covered with a full- and partial-shell of Cu. The exposed portion of the Pt core preferentially binds CO and the Cu shell binds O2, supplying oxygen for the reaction. The Pt-Cu interface provides CO-oxidation sites that are not poisoned by either CO or O2. Additional computational screening shows that this separation of reactant binding sites is possible for several other core@shell NPs. Our results indicate that the metal-metal interface within a single NP can be optimized for design of bifunctional catalytic systems with improved performance.

Evenly transferred single-layered graphene membrane assisted by strong substrate adhesion.

We explored the transfer of a single-layered graphene membrane assisted by substrate adhesion. A relatively larger adhesion force was measured on the SiO2 substrate compared with its van der Waals contribution, which is expected to result from the additional contribution of the chemical bonding force. Density functional theory calculations verified that the strong adhesion force was indeed accompanied by chemical bonding. The transfer of single-layered graphene and subsequent deposition of the dielectric layer were best performed on the SiO2 substrate exhibiting a larger adhesion force. This study suggests the selection and/or modification of the underlying substrate for proper transfer of graphene as well as other 2D materials similar to graphene.

Hypertension caused by renal arteriovenous fistula.

We describe a case of secondary hypertension caused by renal arteriovenous fistula. An 8-year old girl was hospitalized with a severe headache, vomiting, and seizure. Renal angiography demonstrated multiple renal arteriovenous fistula and increased blood renin concentration in the left renal vein. Thus, left renal arteriovenous fistula and renin induced secondary hypertension were diagnosed. Her blood pressure was well controlled by medication with angiotensin converting enzyme inhibitor.