Synergistic growth of nickel and platinum nanoparticles via exsolution and surface reaction.

Bimetallic catalysts combining precious and earth-abundant metals in well designed nanoparticle architectures can enable cost efficient and stable heterogeneous catalysis. Here, we present an interaction-driven in-situ approach to engineer finely dispersed Ni decorated Pt nanoparticles (1-6 nm) on perovskite nanofibres via reduction at high temperatures (600-800 oC). Deposition of Pt (0.5 wt%) enhances the reducibility of the perovskite support and promotes the nucleation of Ni cations via metal-support interaction, thereafter the Ni species react with Pt forming alloy nanoparticles, with the combined processes yielding smaller nanoparticles that either of the contributing processes. Tuneable uniform Pt-Ni nanoparticles are produced on the perovskite surface, yielding reactivity and stability surpassing 1 wt.% Pt/γ-Al2O3 catalysts for CO oxidation. This approach heralds the possibility of in-situ fabrication of supported bimetallic nanoparticles with engineered compositional distributions and performance.

In-situ physical and chemical remediation of Cd and Pb contaminated mine soils cultivated with Chinese cabbage: A three-year field study.

Soils pollution with heavy metals (HMs) is a serious concern due to their toxic effects on crop yield, crop quality, soil environment, and human health. In the current study, four stabilizers of calcium carbonate (CC), dolomite (DL), zeolite (ZL), and steel slag (SS) were applied to cadmium (Cd) and lead (Pb)-contaminated soils as in-situ chemical remediation techniques along with in-situ physical remediation techniques i.e. soil covering (SC) and soil dilution (SD) under real field conditions. For three years, Chinese cabbage (Brassica rapa L.) was grown on the amended fields to examine how the amendments impacted Cd and Pb uptake in plants. The stabilization efficiency of SS, CC, and SC were 75.7 %, 66.0 %, and 71.1 %, respectively, for Cd, and 55.6 %, 55.6 %, and 70.0 %, respectively, for Pb. Results indicated that stabilizer soil amendments significantly decreased the exchangeable (F1) and carbonates bound (F2) fractions of both Cd and Pb. For instance, F1 fraction of Cd decreased from 10.2 (control) to 1.8-2.9 % (with stabilizers). The stabilizers increased Chinese cabbage dry weight by 11.4-22.5 % and decreased Cd and Pb uptake by 67.4 % and 24 %, respectively. The results demonstrated that in-situ chemical remediation technique showed promising results and maintained its efficiency for more than 130 weeks. Current study indicated that chemical remediation of Cd and Pb contaminated soil is more effective and last longer than physical remediation.

Effective single web-structured electrode for high membrane electrode assembly performance in polymer electrolyte membrane fuel cell.

To achieve a sustainable society, CO2 emissions must be reduced and efficiency of energy systems must be enhanced. The polymer electrolyte membrane fuel cell (PEMFC) has zero CO2 emissions and high effectiveness for various applications. A well-designed membrane electrolyte assembly (MEA) composed of electrode layers of effective materials and structure can alter the performance and durability of PEMFC. We demonstrate an efficient electrode deposition method through a well-designed carbon single web with a porous 3D web structure that can be commercially adopted. To achieve excellent electrochemical properties, active Pt nanoparticles are controlled by a nanoglue effect on a highly graphitized carbon surface. The developed MEA exhibits a notable maximum power density of 1082 mW/cm2 at 80°C, H2/air, 50% RH, and 1.8 atm; low cathode loading of 0.1 mgPt/cm2; and catalytic performance decays of only 23.18 and 13.42% under commercial-based durability protocols, respectively, thereby achieving all desirables for commercial applications.

Biofunctional Layered Double Hydroxide Nanohybrids for Cancer Therapy.

Layered double hydroxides (LDHs) with two-dimensional nanostructure are inorganic materials that have attractive advantages such as biocompatibility, facile preparation, and high drug loading capacity for therapeutic bioapplications. Since the intercalation chemistry of DNA molecules into the LDH materials were reported, various LDH nanohybrids have been developed for biomedical drug delivery system. For these reasons, LDHs hybridized with numerous therapeutic agents have a significant role in cancer imaging and therapy with targeting functions. In this review, we summarized the recent advances in the preparation of LDH nanohybrids for cancer therapeutic strategies including gene therapy, chemotherapy, immunotherapy, and combination therapy.

Bifunctional 1,2,4-Triazole/12-Tungstophosphoric Acid Composite Nanoparticles for Biodiesel Production.

Here, a composite nanoparticle with an acid-base bifunctional structure has been reported for the transesterification of rapeseed oil to produce biodiesel. Triazole-PWA (PWA = 12-tungstophosphoric acid) composite materials with a hexahedral structure are produced using the precipitation method, showing the average particle diameters of 200-800 nm. XPS and FT-IR analyses indicate well-defined chemical bonding of triazole moieties to the PWA. The functionalization and immobilization of PWAs are investigated due to strong interactions with triazole, which significantly improves the thermal stability and even surface area of the heteropoly acid. Furthermore, various ratios of triazole and PWAs are examined using NH3-TPD and CO2-TPD to optimize the bi-functionality of acidity and basicity. The prepared nanomaterials are evaluated during the transesterification of rapeseed oil with methanol to analyze the effect of triazole addition to PWAs according to the different ratios. Overall, the bifunctional triazole-PWA composite nanoparticles exhibit higher fatty acid methyl ester (FAME) conversions than pure PWA nanoparticles. The optimized catalyst with a triazole:PWA ratio of 6:1 exhibits the best FAME-conversion performance due to its relatively large surface area, balance of acidity, and strong basicity from the well-designed chemical nano-structure.

In Situ Control of the Eluted Ni Nanoparticles from Highly Doped Perovskite for Effective Methane Dry Reforming.

To design metal nanoparticles (NPs) on a perovskite surface, the exsolution method has been extensively used for efficient catalytic reactions. However, there are still the challenges of finding a combination and optimization for the NPs' control. Thus, we report in situ control of the exsolved Ni NPs from perovskite to apply as a catalyst for dry reforming of methane (DRM). The La0.8Ce0.1Ti0.6Ni0.4O3 (LCTN) is designed by Ce doping to incorporate high amounts of Ni in the perovskite lattice and also facilitate the exsolution phenomenon. By control of the eluted Ni NPs through exsolution, the morphological properties of exsolved Ni NPs are observed to have a size range of 10~49 nm, while the reduction temperatures are changed. At the same time, the chemical structure of the eluted Ni NPs is also changed by an increased reduction temperature to a highly metallic Ni phase with an increased oxygen vacancy at the perovskite oxide surface. The optimized composite nanomaterial displays outstanding catalytic performance of 85.5% CH4 conversion to produce H2 with a value of 15.5 × 1011 mol/s·gcat at 60.2% CO conversion, which shows the importance of the control of the exsolution mechanism for catalytic applications.

Nano-Composite Filler of Heteropolyacid-Imidazole Modified Mesoporous Silica for High Temperature PEMFC at Low Humidity.

Nano-composite filler has received attention for the application to high temperature and low humidity polymer electrolyte membrane (PEM) in fuel cell systems. Heteropolyacids (HPAs) are one of the most attractive materials because of their conductive and thermally stable properties, but have practical limitations due to their high solubility. We investigated the stabilization of HPA on imidazole modified mesoporous silica as a nano-composite filler. The role of mesoporous silica as a support for imidazole and the distribution of chemically bonded HPA on the surface were both confirmed through physical and chemical analysis. The developed nano-composite was utilized to a PEM as a proton conducting filler, cast with commercial AquivionTM solution. Changing the HPA: imidazole ratio and HPA wt%, the composite membrane of Im10/PWA6/Si-MCM-41 (PWA 10 wt%) resulted in higher proton conductivity compared to the non-modified membrane at all operation conditions, especially at high temperature (140 °C) and low relative humidity (RH 10%), with values of 0.3530 and 0.0241 S/m, respectively. A single cell test at H2/Air also showed the effect of adding the nano-composite filler at a wide range of temperatures, which outperformed a single cell with a pristine membrane even at an extremely low humidity condition.

Platinum incorporation into titanate perovskites to deliver emergent active and stable platinum nanoparticles.

Platinum functions exceptionally well as a nanoparticulate catalyst in many important fields, such as in the removal of atmospheric pollutants, but it is scarce, expensive and not always sufficiently durable. Here, we report a perovskite system in which 0.5 wt% Pt is integrated into the support and its subsequent conversion through exsolution to achieve a resilient catalyst. Owing to the instability of most Pt oxides at high temperatures, a thermally stable platinum oxide precursor, barium platinate, was used to preserve the platinum as an oxide during the solid-state synthesis in an approach akin to the Trojan horse legend. By tailoring the procedure, it is possible to produce a uniform equilibrated structure with active emergent Pt nanoparticles strongly embedded in the perovskite surface that display better CO oxidation activity and stability than those of conventionally prepared Pt catalysts. This catalyst was further evaluated for a variety of reactions under realistic test environments-CO and NO oxidation, diesel oxidation catalysis and ammonia slip reactions were investigated.

Molecular Characteristics of Light Cycle Oil Hydrodesulfurization over Silica-Alumina-Supported NiMo Catalysts.

A detailed understanding of the catalytic upgrading of light cycle oil (LCO) is important to achieve effective deep hydrodesulfurization (HDS) when LCO is mixed with straight run gas oil in the diesel pool. Herein, HDS of polyaromatic-rich LCO was studied at the molecular level over three NiMo catalysts on silica-alumina supports, which were synthesized on the pilot scale using different silica/alumina mixing procedures. Gas chromatography with atomic emission detection and two-dimensional gas chromatography with time-of-flight mass spectrometry were used to evaluate the HDS performance through determining the feed and product compositions, respectively, at the molecular level. Furthermore, the textural properties of the catalysts were evaluated using Raman spectroscopy, transmission electron microscopy, and the temperature-programmed desorption of NH3. The performance of the best catalyst was attributed to its higher content of octahedrally coordinated Mo oxide species, a lower number of layered stacks, and the more acidic sites on the surface. In addition, the hydrotreating reactivity of various family groups in LCO over the catalyst was investigated.

Oxide-Carbon Nanofibrous Composite Support for a Highly Active and Stable Polymer Electrolyte Membrane Fuel-Cell Catalyst.

Well-designed electronic configurations and structural properties of electrocatalyst alter the activity, stability, and mass transport for enhanced catalytic reactions. We introduce a nanofibrous oxide-carbon composite by an in situ method of carbon nanofiber (CNF) growth by highly dispersed Ni nanoparticles that are exsoluted from a NiTiO3 surface. The nanofibrous feature has a 3D web structure with improved mass-transfer properties at the electrode. In addition, the design of the CNF/TiO2 support allows for complex properties for excellent stability and activity from the TiO2 oxide support and high electric conductivity through the connected CNF, respectively. Developed CNF/TiO2-Pt nanofibrous catalyst displays exemplary oxygen-reduction reaction (ORR) activity with significant improvement of the electrochemical surface area. Moreover, exceptional resistance to carbon corrosion and Pt dissolution is proven by durability-test protocols based on the Department of Energy. These results are well-reflected to the single-cell tests with even-better performance at the kinetic zone compared to the commercial Pt/C under different operation conditions. CNF/TiO2-Pt displays an enhanced active state due to the strong synergetic interactions, which decrease the Pt d-band vacancy by electron transfer from the oxide-carbon support. A distinct reaction mechanism is also proposed and eventually demonstrates a promising example of an ORR electrocatalyst design.

Interface-designed Membranes with Shape-controlled Patterns for High-performance Polymer Electrolyte Membrane Fuel Cells.

Polymer electrolyte membrane fuel cell is a promising zero-emission power generator for stationary/automotive applications. However, key issues, such as performance and costs, are still remained for an economical commercialization. Here, we fabricated a high-performance membrane electrode assembly (MEA) using an interfacial design based on well-arrayed micro-patterned membranes including circles, squares and hexagons with different sizes, which are produced by a facile elastomeric mold method. The best MEA performance is achieved using patterned Nafion membrane with a circle 2 µm in size, which exhibited a very high power density of 1906 mW/cm(2) at 75 °C and Pt loading of 0.4 mg/cm(2) with 73% improvement compared to the commercial membrane. The improved performance are attributed to the decreased MEA resistances and increased surface area for higher Pt utilization of over 80%. From these enhanced properties, it is possible to operate at lower Pt loading of 0.2 mg/cm(2) with an outstanding performance of 1555 mW/cm(2) and even at air/low humidity operations.

Hollow fibers networked with perovskite nanoparticles for H2 production from heavy oil.

Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2-rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr(0.8)Ru(0.2)O3, LaCr(0.8)Ru(0.1)Ni(0.1)O3, and LaCr(0.8)Ni(0.2)O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ≈50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds.

Pt nanoparticle-reduced graphene oxide nanohybrid for proton exchange membrane fuel cells.

A platinum nanoparticle-reduced graphene oxide (Pt-RGO) nanohybrid for proton exchange membrane fuel cell (PEMFC) application was successfully prepared. The Pt nanoparticles (Pt NPs) were deposited onto chemically converted graphene nanosheets via ethylene glycol (EG) reduction. According to the powder X-ray diffraction (XRD) pattern and transmission electron microscopy (TEM) analysis, the face-centered cubic Pt NPs (3-5 nm in diameter) were homogeneously dispersed on the RGO nanosheets. The electrochemically active surface area and PEMFC power density of the Pt-RGO nanohybrid were determined to be 33.26 m2/g and 480 mW/cm2 (maximum values), respectively, at 75 degrees C and at a relative humidity (RH) of 100% in a single-cell test experiment.