Accelerating metal nanoparticle exsolution by exploiting tolerance factor of perovskite stannate.

The octahedral symmetry in ionic crystals can play a critical role in atomic nucleation and migration during solid-solid phase transformation. Similarly, octahedron distortion, which is characterized by Goldschmidt tolerance factor, strongly influences the exsolution kinetics in the perovskite lattice framework during high-temperature annealing. However, a fundamental study on manipulating the exsolution process by octahedron distortion is still lacking. In this study, we accelerate Ni metal exsolution on the surface of perovskite stannates by increasing the [BO6] octahedron distortion in the lattices. Decreasing the A-site ionic radius (rBa2+ = 161 pm → rSr2+ = 144 pm → rCa2+ = 134 pm) increased the density of exsolved Ni nanoparticles by up to 640% (i.e., 47 particles µm-2 of Ba(Sn, Ni)O3 → 304 particles µm-2 of Ca(Sn, Ni)O3) after the identical exsolution process. Based on the theoretical calculation and experimental characterization, the decrease in crystal symmetry by octahedral distortion promoted the Ni exsolution owing to the boosted Ni migration by weakening the bond strength and generating domain boundaries. The findings highlight the importance of octahedral distortion to control atomic migration through the perovskite lattice framework and provide a strategy to tailor the density of uniformly populated nanoparticles in nanocomposite oxides for multifunctional material design.

Electronic Activation during Nanoparticle Exsolution for Enhanced Activity at Elevated Temperature.

Nanoparticle (NP) exsolution from perovskite-based oxides matrix upon reduction has emerged as an ideal platform for designing highly active catalysts for energy and environmental applications. However, the mechanism of how the material characteristics impacts the activity is still ambiguous. In this work, taking Pr0.4Sr0.6Co0.2Fe0.7Nb0.1O3 thin film as the model system, we demonstrate the critical impact of the exsolution process on the local surface electronic structure. Combining advanced microscopic and spectroscopic techniques, particularly scanning tunneling microscopy/spectroscopy and synchrotron-based near ambient X-ray photoelectron spectroscopy, we find that the band gaps of both the oxide matrix and exsolved NP decrease during exsolution. Such changes are attributed to the defect state within the forbidden band introduced by oxygen vacancies and the charge transfer across the NP/matrix interface. Both the electronic activations of oxide matrix and the exsolved NP phase lead to good electrocatalytic activity toward the fuel oxidation reaction at elevated temperature.

Boosting Pseudocapacitive Behavior of Supercapattery Electrodes by Incorporating a Schottky Junction for Ultrahigh Energy Density.

Pseudo-capacitive negative electrodes remain a major bottleneck in the development of supercapacitor devices with high energy density because the electric double-layer capacitance of the negative electrodes does not match the pseudocapacitance of the corresponding positive electrodes. In the present study, a strategically improved Ni-Co-Mo sulfide is demonstrated to be a promising candidate for high energy density supercapattery devices due to its sustained pseudocapacitive charge storage mechanism. The pseudocapacitive behavior is enhanced when operating under a high current through the addition of a classical Schottky junction next to the electrode-electrolyte interface using atomic layer deposition. The Schottky junction accelerates and decelerates the diffusion of OH‒/K+ ions during the charging and discharging processes, respectively, to improve the pseudocapacitive behavior. The resulting pseudocapacitive negative electrodes exhibits a specific capacity of 2,114 C g-1 at 2 A g-1 matches almost that of the positive electrode's 2,795 C g-1 at 3 A g-1. As a result, with the equivalent contribution from the positive and negative electrodes, an energy density of 236.1 Wh kg-1 is achieved at a power density of 921.9 W kg-1 with a total active mass of 15 mg cm-2. This strategy demonstrates the possibility of producing supercapacitors that adapt well to the supercapattery zone of a Ragone plot and that are equal to batteries in terms of energy density, thus, offering a route for further advances in electrochemical energy storage and conversion processes.

Precise Modulation of Triple-Phase Boundaries towards a Highly Functional Exsolved Catalyst for Dry Reforming of Methane under a Dilution-Free System.

Dry reforming of methane (DRM) has been emerging as a viable solution to achieving carbon neutrality enhanced by the Paris Agreement as it converts the greenhouse gases of CO2 and CH4 into industrially useful syngas. However, there have been limited studies on the DRM catalyst under mild operating conditions with a high dilution gas ratio due to their deactivation from carbon coking and metal sintering. Herein, we apply the triple-phase boundary (TPB) concept to DRM catalyst via exsolution phenomenon that can secure elongated TPB by controlling the Fe-doping ratio in perovskite oxide. Remarkably, the exsolved catalyst with prolongated TPB shows exceptional CO2 and CH4 conversion rates of 95.9 % and 91.6 %, respectively, stable for 1000 hours under a dilution-free system. DFT calculations confirm that the Lewis acid of support and Lewis base of metal at the TPB promote the adsorption of reactants, resulting in lowering the overall CO2 dissociation and CH4 dehydrogenation energy.

Unveiling the key factor for the phase reconstruction and exsolved metallic particle distribution in perovskites.

To significantly increase the amount of exsolved particles, the complete phase reconstruction from simple perovskite to Ruddlesden-Popper (R-P) perovskite is greatly desirable. However, a comprehensive understanding of key parameters affecting the phase reconstruction to R-P perovskite is still unexplored. Herein, we propose the Gibbs free energy for oxygen vacancy formation in Pr0.5(Ba/Sr)0.5TO3-δ (T = Mn, Fe, Co, and Ni) as the important factor in determining the type of phase reconstruction. Furthermore, using in-situ temperature & environment-controlled X-ray diffraction measurements, we report the phase diagram and optimum 'x' range required for the complete phase reconstruction to R-P perovskite in Pr0.5Ba0.5-xSrxFeO3-δ system. Among the Pr0.5Ba0.5-xSrxFeO3-δ, (Pr0.5Ba0.2Sr0.3)2FeO4+δ - Fe metal demonstrates the smallest size of exsolved Fe metal particles when the phase reconstruction occurs under reducing condition. The exsolved nano-Fe metal particles exhibit high particle density and are well-distributed on the perovskite surface, showing great catalytic activity in fuel cell and syngas production.

Activating Lattice Oxygen in Perovskite Oxide by B-Site Cation Doping for Modulated Stability and Activity at Elevated Temperatures.

Doping perovskite oxide with different cations is used to improve its electro-catalytic performance for various energy and environment devices. In this work, an activated lattice oxygen activity in Pr0.4 Sr0.6 Cox Fe0.9- x Nb0.1 O3- δ (PSCxFN, x = 0, 0.2, 0.7) thin film model system by B-site cation doping is reported. As Co doping level increases, PSCxFN thin films exhibit higher concentration of oxygen vacancies ( V o • • ) as revealed by X-ray diffraction and synchrotron-based X-ray photoelectron spectroscopy. Density functional theory calculation results suggest that Co doping leads to more distortion in FeO octahedra and weaker metaloxygen bonds caused by the increase of antibonding state, thereby lowering V o • • formation energy. As a consequence, PSCxFN thin film with higher Co-doping level presents larger amount of exsolved particles on the surface. Both the facilitated V o • • formation and B-site cation exsolution lead to the enhanced hydrogen oxidation reaction (HOR) activity. Excessive Co doping until 70%, nevertheless, results in partial decomposition of thin film and degrades the stability. Pr0.4 Sr0.6 (Co0.2 Fe0.7 Nb0.1 )O3 with moderate Co doping level displays both good HOR activity and stability. This work clarifies the critical role of B-site cation doping in determining the V o • • formation process, the surface activity, and structure stability of perovskite oxides.

Dopant-Driven Positive Reinforcement in Ex-Solution Process: New Strategy to Develop Highly Capable and Durable Catalytic Materials.

The ex-solution phenomenon, a central platform for growing metal nanoparticles on the surface of host oxides in real time with high durability and a fine distribution, has recently been applied to various scientific and industrial fields, such as catalysis, sensing, and renewable energy. However, the high-temperature processing required for ex-solutions (>700 °C) limits the applicable material compositions and has hindered advances in this technique. Here, an unprecedented approach is reported for low-temperature particle ex-solution on important nanoscale binary oxides. WO3 with a nanosheet structure is selected as the parent oxide, and Ir serves as the active metal species that produces the ex-solved metallic particles. Importantly, Ir doping facilitates a phase transition in the WO3 bulk lattice, which further promotes Ir ex-solution at the oxide surface and eventually enables the formation of Ir particles (<3 nm) at temperatures as low as 300 °C. Low-temperature ex-solution effectively inhibits the agglomeration of WO3 sheets while maintaining well-dispersed ex-solved particles. Furthermore, the Ir-decorated WO3 sheets show excellent durability and H2 S selectivity when used as sensing materials, suggesting that this is a generalizable synthetic strategy for preparing highly robust heterogeneous catalysts for a variety of applications.

Metabolic changes of Phomopsis longicolla fermentation and its effect on antimicrobial activity against Xanthomonas oryzae.

Bacterial blight, an important and potentially destructive bacterial disease in rice caused by Xanthomonas oryzae pv. oryzae (Xoo), has recently developed resistance to the available antibiotics. In this study, mass spectrometry (MS)-based metabolite profiling and multivariate analysis were employed to investigate the correlation between time-dependent metabolite changes and antimicrobial activities against Xoo over the course of Phomopsis longicolla S1B4 fermentation. Metabolites were clearly differentiated based on fermentation time into phase 1 (days 4-8) and phase 2 (days 10-20) in the principal component analysis (PCA) plot. The multivariate statistical analysis showed that the metabolites contributing significantly for phases 1 and 2 were deacetylphomoxanthone B, monodeacetylphomoxanthone B, fusaristatin A, and dicerandrols A, B, and C as identified by liquid chromatography-mass spectrometry (LC-MS), and dimethylglycine, isobutyric acid, pyruvic acid, ribofuranose, galactofuranose, fructose, arabinose, hexitol, myristic acid, and propylstearic acid were identified by gas chromatography-mass spectrometry (GC-MS)-based metabolite profiling. The most significantly different secondary metabolites, especially deacetylphomoxanthone B, monodeacetylphomoxanthone B, and dicerandrol A, B and C, were positively correlated with antibacterial activity against Xoo during fermentation.

Evaluation of struvite obtained from semiconductor wastewater as a fertilizer in cultivating Chinese cabbage.

The present work evaluated the fertilizing value of struvite deposit recovered from semiconductor wastewater in cultivating Chinese cabbage. The fertilizing effect of struvite deposit was compared with that of commercial fertilizers: complex, organic and compost. Laboratory pot test results clearly showed that the growth of Chinese cabbage was better promoted when the struvite deposit was used than with organic and compost fertilizers even though complex fertilizer was the most effective in growing Chinese cabbage. It was revealed that potassium (K) was a key element in the determination of growth rate of Chinese cabbage. Also, the abundant nutrients such as nitrogen (N), phosphorus (P), K, calcium (Ca) and magnesium (Mg) were observed in the vegetable tissue of struvite pot. Specifically, P was the most-founded component in the vegetable tissue of struvite pot. Meanwhile, the utilization of struvite as a fertilizer led to the lowest accumulation of copper (Cu) and no detection of cadmium (Cd), arsenic (As), lead (Pb) and nickel (Ni) in the Chinese cabbage. It was found that the optimum struvite dosage for the cultivation of Chinese cabbage was 1.6 g struvite/kg soil. Based on these findings, it was concluded that the struvite deposits recovered from semiconductor wastewater were effective as a multi-nutrient fertilizer for Chinese cabbage cultivation.

Ultrafast surface enhanced resonance Raman scattering detection in droplet-based microfluidic systems.

The development of ultrafast Raman-based detection is one of the most interesting challenges underpinning the application of droplet-based microfluidics. Herein, we describe the use of surface-enhanced resonance Raman spectroscopy (SERRS) with submillisecond time resolution as a powerful detection tool in microdroplet reactors. Individual droplets containing silver nanoparticle aggregates functionalized with Raman reporters are interrogated and characterized by full spectra acquisitions with high spatial resolution in real time. Whereas previous works coupling SERRS with droplet-based microfluidics acquire a single spectrum over single or multiple droplets, we build upon these results by increasing our temporal resolution by 2 orders of magnitude. This allows us to interrogate multiple points within one individual droplet. The SERRS signals emitted from the aggregates are utilized to access the influence of flow rate on droplet size and throughput. Accordingly, our approach allows for high-throughput analysis that facilitates the study of other biological assays or molecular interactions.

Reichenbachiella faecimaris sp. nov., isolated from a tidal flat, and emended descriptions of the genus Reichenbachiella and Reichenbachiella agariperforans.

A taxonomic study was carried out on two bacterial strains, PCP11(T) and PCP104, isolated from a tidal flat of the Yellow Sea, Korea. Comparative 16S rRNA gene sequence studies showed that these strains belonged to the family Cytophagaceae, phylum Bacteroidetes. Strains PCP11(T) and PCP104 shared 99.4 % sequence similarity and were related most closely to Reichenbachiella agariperforans KMM 3525(T) (95.8 and 96.0 % sequence similarity, respectively). Members of the genera Fulvivirga, Roseivirga, Fabibacter and Marinoscillum were the next closest relatives of the new isolates, with sequence similarities ≤ 91 %. The two isolates were Gram-staining-negative, strictly aerobic, gliding bacteria. They grew in the presence of 1-5 % NaCl, at pH 5.5-8.5 and at 4-35 °C. Strains PCP11(T) and PCP104 shared a number of physiological and biochemical properties with Reichenbachiella agariperforans KMM 3525(T), but they differed from this strain in the hydrolysis of biopolymers and in the production of carotenoid and flexirubin-type pigments. Both strains possessed iso-C(15 : 0), summed feature 4 (C(16 : 1)ω7c and/or iso-C(15 : 0) 2-OH) and C(15 : 0) as major cellular fatty acids. The major respiratory quinone was menaquinone 7 (MK-7). The G+C contents of the genomic DNA of strains PCP11(T) and PCP104 were 39.6 and 41.9 mol%, respectively. On the basis of phenotypic data and phylogenetic inference, it is proposed that the two isolates represent a novel species, Reichenbachiella faecimaris sp. nov., with strain PCP11(T) ( = KACC 14523(T)  = JCM 16588(T)) as the type strain. Emended descriptions of the genus Reichenbachiella and Reichenbachiella agariperforans are also proposed.

Pseudoalteromonas donghaensis sp. nov., isolated from seawater.

A Gram-negative, rod-shaped, motile and aerobic bacterium, designated strain HJ51(T), was isolated from a seawater sample from the East Sea, near South Korea. The isolate grew slowly at 4 °C, was able to grow at 40 °C, required NaCl and grew optimally at pH 6.5-7.0. The G+C content of the genomic DNA was 41.8 mol%. The major fatty acids were summed feature 4 (C(16 : 1)ω7c and/or iso-C(15 : 0) 2-OH), C(16 : 0) and summed feature 7 (C(18 : 1)ω7c, C(18 : 1)ω9t and/or C(18 : 1)ω12t). Phylogenetic analysis based on 16S rRNA gene sequences revealed that strain HJ51(T) belonged to the genus Pseudoalteromonas and had 91.7-98.9 % 16S rRNA gene sequence similarity with type strains of species of the genus Pseudoalteromonas. Strain HJ51(T) had 7.2 % DNA-DNA relatedness with Pseudoalteromonas mariniglutinosa DSM 15203(T) and 12.9 % with Pseudoalteromonas prydzensis DSM 14232(T). On the basis of the phenotypic, phylogenetic and genomic data, strain HJ51(T) represents a novel species of the genus Pseudoalteromonas, for which the name Pseudoalteromonas donghaensis sp. nov. is proposed. The type strain is HJ51(T) (=KCTC 22219(T)=LMG 24469(T)).

Flavobacterium chungbukense sp. nov., isolated from soil.

A yellow-pigmented, Gram-staining-negative, non-motile, strictly aerobic and rod-shaped bacterium, designated CS100(T), was isolated from soil in Chungbuk, Korea. Phylogenetic analysis and comparative studies based on the 16S rRNA gene sequence showed that strain CS100(T) belonged to the genus Flavobacterium in the family Flavobacteriaceae. Strain CS100(T) showed the highest sequence similarities to Flavobacterium glaciei JCM 13953(T) (97.6 %) and Flavobacterium johnsoniae KACC 11410(T) (97.1 %). Sequence similarity to other members of the genus Flavobacterium was 91.5-97.0 %. Growth occurred at 4-30 °C, at pH 5.0-9.0 and in the presence of 0-2 % (w/v) NaCl. Flexirubin-type pigments were produced. Menaquinone-6 (MK-6) was the major respiratory quinone and the major fatty acids were iso-C(15 : 0) (17.3 %), summed feature 3 (comprising iso-C(15 : 0) 2-OH and/or C(16 : 1)ω7c, 15.5 %) and C(16 : 0) (11.8 %). The DNA G+C content was 36.4 mol%. Strain CS100(T) hydrolysed skimmed milk and gelatin, but not chitin or pectin, and showed oxidase and catalase activities. DNA-DNA relatedness was 3.0 % with F. glaciei JCM 13953(T) and 11.5 % with F. johnsoniae KACC 11410(T). On the basis of the evidence from this study, strain CS100(T) represents a novel species of the genus Flavobacterium, for which the name Flavobacterium chungbukense sp. nov. is proposed. The type strain is CS100(T) ( = KACC 15048(T) = JCM 17386(T)).

On-chip immunoassay using surface-enhanced Raman scattering of hollow gold nanospheres.

A surface-enhanced Raman scattering (SERS)-based gradient optofluidic sensor has been developed for a fast and sensitive immunoassay. In this work, a novel microfluidic sensor with functional internal structures has been designed and fabricated. This sensor is composed of three compartments consisting of the gradient channel that serially dilutes the target marker, the injection and mixing area of antibody-conjugated hollow gold nanospheres and magnetic beads, and the trapping area of sandwich immunocomplexes using multiple solenoids. Quantitative analysis of a specific target marker is performed by analyzing its characteristic SERS signals. This SERS-based gradient optofluidic sensor can replace the set of microwells or microtubes used in manual serial dilutions that have been traditionally used in enzyme-linked immunosorbent assay (ELISA)-type assays. The limit of detection for rabbit immunoglobin (IgG) is estimated to be 1-10 ng/mL. This novel SERS-based optofluidic immunoassay system is expected to be a powerful clinical tool for the fast and sensitive medical diagnosis of a disease.

Optofluidic platforms based on surface-enhanced Raman scattering.

We report recent progress in the development of surface-enhanced Raman scattering (SERS)-based optofluidic platforms for the fast and sensitive detection of chemical and biological analytes. In the current context, a SERS-based optofluidic platform is defined as an integrated analytical device composed of a microfluidic element and a sensitive Raman spectrometer. Optofluidic devices for SERS detection normally involve nanocolloid-based microfluidic systems or metal nanostructure-embedded microfluidic systems. In the current review, recent advances in both approaches are surveyed and assessed. Additionally, integrated real-time sensing systems that combine portable Raman spectrometers with microfluidic devices are also reviewed. Such real-time sensing systems have significant utility in environmental monitoring, forensic science and homeland defense applications.

Identification, fermentation, and bioactivity against Xanthomonas oryzae of antimicrobial metabolites isolated from Phomopsis longicolla S1B4.

Bacterial blight, an important and potentially destructive bacterial disease in rice, is caused by Xanthomonas oryzae. Recently, this organism has developed resistance to available antibiotics, prompting scientists to find a suitable alternative. This study focused on secondary metabolites of Phomopsis longicolla to target X. oryzae. Five bioactive compounds were isolated by activity-guided fractionation from ethyl acetate extracts of mycelia and were identified by LC/MS and NMR spectroscopy as dicerandrol A, dicerandrol B, dicerandrol C, deacetylphomoxanthone B, and fusaristatin A. This is the first time fusaristatin A has been isolated from Phomopsis sp. Deacetylphomoxanthone B showed a higher antibacterial effect against X. oryzae KACC 10331 than the positive control (2,4-diacetyphloroglucinol). Dicerandrol A also showed high antimicrobial activity against Grampositive bacteria (Staphylococcus aureus, Bacillus subtilis) and yeast (Candida albicans). In addition, high production yields of these compounds were obtained at the stationary and death phases.

Surface-enhanced Raman scattering in nanoliter droplets: towards high-sensitivity detection of mercury (II) ions.

We report a new method for the trace analysis of mercury (II) ions in water. The approach involves the use of droplet-based microfluidics combined with surface-enhanced Raman scattering (SERS) detection. This novel combination provides both fast and sensitive detection of mercury (II) ions in water. Specifically, mercury (II) ion detection is performed by using the strong affinity between gold nanoparticles and mercury (II) ions. This interaction causes a change in the SERS signal of the reporter molecule rhodamine B that is a function of mercury (II) ion concentration. To allow both reproducible and quantitative analysis, aqueous samples are encapsulated within nanoliter-sized droplets. Manipulation of such droplets through winding microchannels affords rapid and efficient mixing of the contents. Additionally, memory effects, caused by the precipitation of nanoparticle aggregates on channel walls, are removed since the aqueous droplets are completely isolated by a continuous oil phase. Quantitative analysis of mercury (II) ions was performed by calculating spectral peak area of rhodamine B at 1,647 cm(-1). Using this approach, the calculated concentration limit of detection was estimated to be between 100 and 500 ppt. Compared with fluorescence-based methods for the trace analysis of mercury (II) ions, the detection sensitivities were enhanced by approximately one order of magnitude. The proposed analytical method offers a rapid and reproducible trace detection capability for mercury (II) ions in water.

A portable surface-enhanced Raman scattering sensor integrated with a lab-on-a-chip for field analysis.

An integrated real-time sensing system that uses a portable Raman spectrometer and a micropillar array chip has been developed for field analysis. The problem of poor detection sensitivity, caused by miniaturization in the portable Raman spectrometer, was overcome by using the surface-enhanced Raman scattering (SERS) technique. The problem of poor reproducibility in the SERS detection, caused by different particle sizes and inhomogeneous degrees of aggregation, was also overcome by using continuous flow and homogeneous mixing between the analytes and nanocolloidal silver in a micropillar array microfluidic chip. Two hazardous materials, dipicolinic acid and malachite green, were quantitatively analysed using our integrated portable Raman sensor system. The observed limit of detection was estimated to be 200 ppb and 500 ppb, respectively. Our proposed analytical method, using a micropillar array PDMS chip and a portable SERS system, offers a rapid and reproducible trace detection capability for hazardous materials in the field.

DNA hybridization detection in a microfluidic channel using two fluorescently labelled nucleic acid probes.

A conceptually new technique for fast DNA detection has been developed. Here, we report a fast and sensitive online fluorescence resonance energy transfer (FRET) detection technique for label-free target DNA. This method is based on changes in the FRET signal resulting from the sequence-specific hybridization between two fluorescently labelled nucleic acid probes and target DNA in a PDMS microfluidic channel. Confocal laser-induced microscopy has been used for the detection of fluorescence signal changes. In the present study, DNA hybridizations could be detected without PCR amplification because the sensitivity of confocal laser-induced fluorescence detection is very high. Two probe DNA oligomers (5'-CTGAT TAGAG AGAGAA-TAMRA-3' and 5'-TET-ATGTC TGAGC TGCAGG-3') and target DNA (3'-GACTA ATCTC TCTCT TACAG GCACT ACAGA CTCGA CGTCC-5') were introduced into the channel by a microsyringe pump, and they were efficiently mixed by passing through the alligator teeth-shaped PDMS microfluidic channel. Here, the nucleic acid probes were terminally labelled with the fluorescent dyes, tetrafluororescein (TET) and tetramethyl-6-carboxyrhodamine (TAMRA), respectively. According to our confocal fluorescence measurements, the limit of detection of the target DNA is estimated to be 1.0 x 10(-6) to 1.0 x 10(-7)M. Our result demonstrates that this analytical technique is a promising diagnostic tool that can be applied to the real-time analysis of DNA targets in the solution phase.