VOx Matrix Confinement Approach to Generate Sub-3 nm L10-Pt-Based Intermetallic Catalysts for Fuel Cell Cathode.

Pt-based intermetallic compounds (IMCs) are considered as a class of promising fuel cell electrocatalysts, owing to their outstanding intrinsic activity and durability. However, the synthesis of uniformly dispersed IMCs with small sizes presents a formidable challenge during the essential high-temperature annealing process. Herein, a facile and generally applicable VOx matrix confinement strategy is demonstrated for the controllable synthesis of ordered L10-PtM (M = Fe, Co, and Mn) nanoparticles, which not only enhances the dispersion of intermetallic nanocrystals, even at high loading (40 wt%), but also simplifies the oxide removal and acid-washing procedures. Taking intermetallic PtCo as an example, the as-prepared catalyst displays a high-performance oxygen reduction activity (mass activity of 1.52 A mgPt -1) and excellent stability in the membrane electrode assemblies (MEAs) (the ECSA has just 7% decay after durability test). This strategy provides an economical and scalable route for the controlled synthesis of Pt-based intermetallic catalysts, which can pave a way for the commercialization of fuel cell technologies.

Size effect of CoS2 cocatalyst on photocatalytic hydrogen evolution performance of g-C3N4.

The main goal of researchers is to obtain cheap cocatalysts that can promote the photocatalytic activity of catalysts. In this work, a series of CoS2/g-C3N4 (denoted as CoS2/CN) composite photocatalysts were synthesized by photodepositing CoS2 on g-C3N4 surface. The size of CoS2 species could be tuned from single-atom to nanometer scale, which had effect on photocatalysis. The 5CoS2/CN sample with proper nano size of CoS2 cocatalyst had the best photocatalytic performance (1707.19 µmol g-1h-1) in producing H2 under visible light irradiation (λ > 420 nm). Its photocatalytic activity was about 1434.6 times higher than that of pure g-C3N4 and almost equal with that of Pt/CN catalyst (1799.54 µmol g-1h-1). The Density Functional Theory (DFT) calculation results further suggested that the ability of accumulating the electrons of the cocatalyst was based on the size effect of CoS2, and the proper size of the cocatalyst efficiently promoted the separation of photogenerated electron-hole pairs.

Boosting the activity and stability via synergistic catalysis of Co nanoparticles and MoC to construct a bifunctional electrocatalyst for high-performance and long-life rechargeable zinc-air batteries.

The high overpotential of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) leading to slow air cathode kinetics is still a major challenge for zinc-air batteries (ZABs), hindering the commercialization of ZABs. With the advantages of cost-effectiveness and feasibility of synthesis at room temperature, zeolite imidazole frameworks (ZIFs) are regarded as advanced precursors. But a majority of ZIF-derived catalysts show only one catalytic activity, which limits their performance in ZABs as well as the cycling stability. In addition, molybdenum carbide (MoC) is recognized as an excellent candidate for renewable energy conversion due to its good chemical resistance and thermal stability. Herein, we report a ZIF-67-derived Co/MoC-NC multiphase doped carbon bifunctional ORR/OER catalyst with multiple active sites for the cathode of ZABs. The synergistic catalysis of Co nanoparticles and MoC nanoparticles in Co/MoC-NC which are embedded in a thin layer of N-doped graphitic carbon and immobilized on N-doped graphitic carbon, respectively, demonstrates superior ORR catalytic performance and durability both under alkaline and acidic conditions (E1/2 = 0.87 V in 1.0 M KOH and E1/2 = 0.76 V in 0.5 M H2SO4). Simultaneously, Co/MoC-NC also exhibits favorable OER performance (10 mA cm-2, η = 320 mV) in 1 M KOH. Furthermore, a remarkable peak-power density of 215.36 mW cm-2 and great cycling stability could be achieved while applying Co/MoC-NC in the cathode of ZABs (over 300 h). This work will provide a viable design concept for designing and synthesizing multifunctional catalysts to construct rechargeable ZABs.

Advantageous Role of Ir0 Supported on TiO2 Nanosheets in Photocatalytic CO2 Reduction to CH4: Fast Electron Transfer and Rich Surface Hydroxyl Groups.

Ir-based heterogeneous catalysts for photocatalytic CO2 reduction have rarely been reported and are worthy of investigation. In this work, TiO2 nanosheets with a higher specific surface area and more oxygen vacancies were employed to support Ir metal by impregnation (Imp) and ethylene glycol (EG) reduction methods. In comparison with Ir/TiO2 (Imp) and TiO2, Ir/TiO2 (EG) exhibited excellent photocatalytic performance toward CO2 reduction, especially for CH4 production on account of the oxygen defect of TiO2 and rich surface hydroxyl groups produced from the interaction between TiO2 nanosheets and metallic Ir. In situ ESR suggested that the oxygen defect was significant for CO2 adsorption/activation. Furthermore, metallic Ir was beneficial for photogenerated electron transfer, surface hydroxyl generation, and adsorption of the CO intermediate, generating more available electrons and reducing agents for CH4 production. In situ CO2 DRIFTS confirmed the key synergistic interaction between the oxygen defect and metallic Ir in the photoreduction from CO2 to CH4.

Hydrodeoxygenation of water-insoluble bio-oil to alkanes using a highly dispersed Pd-Mo catalyst.

Bio-oil, produced by the destructive distillation of cheap and renewable lignocellulosic biomass, contains high energy density oligomers in the water-insoluble fraction that can be utilized for diesel and valuable fine chemicals productions. Here, we show an efficient hydrodeoxygenation catalyst that combines highly dispersed palladium and ultrafine molybdenum phosphate nanoparticles on silica. Using phenol as a model substrate this catalyst is 100% effective and 97.5% selective for hydrodeoxygenation to cyclohexane under mild conditions in a batch reaction; this catalyst also demonstrates regeneration ability in long-term continuous flow tests. Detailed investigations into the nature of the catalyst show that it combines hydrogenation activity of Pd and high density of both Brønsted and Lewis acid sites; we believe these are key features for efficient catalytic hydrodeoxygenation behavior. Using a wood and bark-derived feedstock, this catalyst performs hydrodeoxygenation of lignin, cellulose, and hemicellulose-derived oligomers into liquid alkanes with high efficiency and yield.Bio-oil is a potential major source of renewable fuels and chemicals. Here, the authors report a palladium-molybdenum mixed catalyst for the selective hydrodeoxygenation of water-insoluble bio-oil to mixtures of alkanes with high carbon yield.

Crystal-plane-dependent metal-support interaction in Au/TiO2.

Metal-support interactions between Au and TiO2 are studied based on Au/TiO2 catalysts with different TiO2 crystal planes exposed. With ex situ XPS, TEM and in situ DRIFTS, we have investigated the crystal-plane-dependent metal-support interaction effects on the physiochemical properties of Au/TiO2 catalysts. Based on the structural characterization and spectroscopic results, we can observe chemical oscillations (including the electronic structures of Au nanoparticles and the interaction between Au/TiO2 catalysts and CO molecules) during alternate H2 and O2 pre-treatments. Their variation tendencies of oscillations are greatly dependent on the crystal planes of TiO2 and the pre-treatment temperature. Furthermore, their surface and electronic changes after H2 and O2 pre-treatments can be well correlated with their catalytic activities in CO oxidation. Electron-transfer processes across the Au-TiO2 interface are proved to be the origin accounting for their changes after H2 and O2 pre-treatments. The different electronic structures of different TiO2 crystal planes should have relationships with the crystal-plane-dependent metal-support interaction effects in Au/TiO2.

Engineering the TiO2 -graphene interface to enhance photocatalytic H2 production.

In this work, TiO2 -graphene nanocomposites are synthesized with tunable TiO2 crystal facets ({100}, {101}, and {001} facets) through an anion-assisted method. These three TiO2 -graphene nanocomposites have similar particle sizes and surface areas; the only difference between them is the crystal facet exposed in TiO2 nanocrystals. UV/Vis spectra show that band structures of TiO2 nanocrystals and TiO2 -graphene nanocomposites are dependent on the crystal facets. Time-resolved photoluminescence spectra suggest that the charge-transfer rate between {100} facets and graphene is approximately 1.4 times of that between {001} facets and graphene. Photoelectrochemical measurements also confirm that the charge-separation efficiency between TiO2 and graphene is greatly dependent on the crystal facets. X-ray photoelectron spectroscopy reveals that Ti-C bonds are formed between {100} facets and graphene, while {101} facets and {001} facets are connected with graphene mainly through Ti-O-C bonds. With Ti-C bonds between TiO2 and graphene, TiO2 -100-G shows the fastest charge-transfer rate, leading to higher activity in photocatalytic H2 production from methanol solution. TiO2 -101-G with more reductive electrons and medium interfacial charge-transfer rate also shows good H2 evolution rate. As a result of its disadvantageous electronic structure and interfacial connections, TiO2 -001-G shows the lowest H2 evolution rate. These results suggest that engineering the structures of the TiO2 -graphene interface can be an effective strategy to achieve excellent photocatalytic performances.

Gene expression responses in different regions of Eisenia fetida with antiparasitic albendazole exposure.

Albendazole (ABZ) is a veterinary drug with a high efficiency against parasite. The aim of this research is to investigate and characterize the response of gene expression in different regions of earthworms Eisenia fetida in relation to ABZ exposure. In this research, the earthworms were exposed to ABZ at 0, 10, 30, 90, and 270 mg/kg concentrations for 42 days. Within the initial 14-day exposure, the expression levels of two target genes (mitochondrial large ribosomal subunit (l-rRNA) and heat shock protein (HSP90)) in different regions of earthworms were affected significantly by the different exposure concentrations of ABZ, but the growth rates were similar among the ABZ and control groups. With longer exposure time, growth rates decreased significantly after 28 days of exposure at 90 and 270 mg/kg. These results of target genes expression suggest that, at low ABZ concentrations, the middle region of earthworms is more sensitive to ABZ than the anterior and posterior regions. In the middle region, the l-rRNA expression of the ABZ-exposed groups was significantly lower than the control group, with a reduction to 23%, 25% and 31% for 10, 30 and 90 mg/kg ABZ concentrations, respectively (P<0.01). In contrast, the HSP90 expression of the ABZ groups (full range of 10 to 270 mg/kg) in the middle region increased 4.1-8.7 folds over the control group (P<0.01). In the anterior and posterior regions, the expression of the two target genes at 10mg/kg did not differ significantly among the ABZ and control groups (P>0.05), except for l-rRNA in the posterior region. The characterization and understanding of target genes expression in different regions of earthworms can provide important information on predictive early reading on the pollution of ABZ residue in soils.

In situ loading of ultra-small Cu2O particles on TiO2 nanosheets to enhance the visible-light photoactivity.

In this work, ultra-small Cu(2)O nanoparticles have been loaded on TiO(2) nanosheets with {001} facets exposed through a one-pot hydrothermal reaction. These Cu(2)O nanoparticles are well-dispersed on TiO(2) nanosheets with narrow size distributions and controllable sizes from 1.5 to 3.0 nm. Through XRD, TEM, N(2) absorption-desorption isotherms and UV-vis diffuse reflectance spectra, the Cu(2)O/TiO(2) nanosheets show similar phase structures, morphologies, pore structures as compared to pure TiO(2) nanosheets. Due to the loading of ultra-small Cu(2)O nanoparticles, heterojunctions are formed between Cu(2)O and TiO(2), which favors the efficient separation of photo-generated electrons and holes. Caused by the electron transfer from Cu(2)O to TiO(2), Cu(2)O/TiO(2) nanosheets show excellent visible-light activity, about 3 times that of N-doped TiO(2) nanosheets with {001} facets exposed. Furthermore, charge transfer rate across the interface of Cu(2)O and TiO(2) shows great dependence on the size of Cu(2)O particles. The charge transfer across the interface may be more efficient between TiO(2) nanosheets and smaller Cu(2)O nanoparticles. Therefore, the Ti : Cu = 30 : 1(atomic ratio) sample shows the best activity due to its balance in light harvest and electron transfer rate in the degradation of phenol under visible light.