Coupling plasmon and catalytic-active hotspots of Au@Pt core-satellite nanoparticles for in-situ spectroscopic observation of plasmon-promoted decarboxylation.

Plasmon-induced hot carriers are a promising "active" energy source, attracting increasing attention for their potential applications in photocatalysis and photodetection. Here, we hybridize plasmonic Au spherical nanoparticles (SNPs) with catalytically active Pt nanocrystals to form Au@Pt core-satellite nanoparticles (CSNPs), which act as both an efficient catalyst for plasmon-promoted decarboxylation reaction and a robust surface-enhanced Raman scattering (SERS) substrate for plasmon-enhanced molecular spectroscopic detection. By regulating the coverage of Pt nanocrystals on the Au SNPs, we modulated the "hotspot" structures of the Au@Pt CSNPs to optimize the SERS detecting capability and catalytic decarboxylation performance. The coupling functionalities enable us with unique opportunities to in-situ SERS monitor universal reactions catalyzed by active catalysts (e.g. Pt, Pd) in the chemical industry in real-time. The decarboxylation rate of 4-mercaptophenylacetic acid was dynamically controlled by the surface catalytic decarboxylation step, following first-order overall reaction kinetics. Moreover, the reaction rate exhibited a strong correlation with the local field enhancement |E/E0|4 of the hotspot structure. This work provides spectroscopic insights into the molecule-plasmon interface under the plasmon-promoted catalytic reactions, guiding the rational design of the plasmonic interface of nanocatalysts to achieve desired functionalities.

Synergistic Combination of Fermi Level Equilibrium and Plasmonic Effect for Formic Acid Dehydrogenation.

Developing an efficient catalyst for formic acid (FA) dehydrogenation is a promising strategy for safe hydrogen storage and transportation. Herein, we successfully developed trimetallic NiAuPd heterogeneous catalysts through a galvanic replacement reaction and a subsequent chemical reduction process to boost hydrogen generation from FA decomposition at room temperature by coupling Fermi level engineering with plasmonic effect. We demonstrated that Ni worked as an electron reservoir to donate electrons to Au and Pd driven by Fermi level equilibrium whereas plasmonic Au served as an optical absorber to generate energetic hot electrons and a charge-redistribution mediator. Ni and Au worked cooperatively to promote the charge heterogeneity of surface-active Pd sites, leading to enhanced chemisorption of formate-related intermediates and eventually outstanding activity (342 mmol g-1 h-1 ) compared with bimetallic counterpart. This work offers excellent insight into the rational design of efficient catalysts for practical hydrogen energy exploitation.

Sorption of phenols and flavonoids on activated charcoal improves protein metabolism, antioxidant status, immunity, and intestinal morphology in broilers.

Previous studies have revealed that activated charcoal sorption of Chinese herbal extracts is more effective than activated charcoal. The present study was designed to investigate whether phenols and flavonoids have an effect on nutrient metabolism, antioxidant activity, immunity, and intestinal morphology in broilers. Seven diets [basal diet (CON); CON supplemented with 450 mg/kg of activated charcoal (AC); CON supplemented with 250, 500, 750, 1,000, or 7,500 mg/kg of phenolic acids and flavonoids (PF) to AC (PFAC)]. PFAC was the complex of AC sorption of PF in the ratio of 9:1. These dietary treatments for broilers lasted for 42 days. Results showed that at d 21, all doses of PFAC altered serum levels of total protein, albumin, and creatinine compared to AC (p < 0.05). Both PFAC and AC altered HDL-, LDL-, and VLDL-cholesterol levels compared to CON (p < 0.05). PFAC at 500 mg/kg (450 mg/kg AC+ 50 mg/kg phenolic acids and flavonoids) increased serum IgA and IgM (p < 0.05), but AC at 450 mg/kg did not, compared to CON. At d 42, breast and thigh muscles of PFAC-treated broilers had higher free radical scavenging activities compared to CON (p < 0.05), but AC had no such effect. PFAC at 500 mg/kg increased villus height in the duodenum, jejunum, and ileum compared to CON (p < 0.05), but AC had no such response. PFAC at 500 mg/kg effectively improved protein and lipid metabolism, antioxidant status, and intestinal morphology, but AC had no such effect at a similar dose. Excessive PFAC (7,500 mg/kg) showed no significant side effects on broiler growth, liver damage, or hematology. These results suggest that phenols and flavonoids, in cooperation with activated charcoal, provide the majority of the functions of the herbal extract from multiple Chinese medicinal herbs.

Molecular Precursor Route to CuCo2S4 Nanosheets: A High-Performance Pre-Catalyst for Oxygen Evolution and Its Application in Zn-Air Batteries.

Development of high-efficiency non-precious metal-based electrocatalysts to drive the complex four-electron process of the oxygen evolution reaction (OER) is crucial for production of hydrogen and energy storage components. Herein, bimetallic CuCo2S4 nanosheets were created by a new molecular precursor route. The optimal CuCo2S4 catalyst demonstrates superior performance to catalyze the OER with excellent stability, which was confirmed by the low overpotential of 290 mV at 10 mA cm-2 in 1 M KOH. The catalytic activity can be maintained for at least 40 h. The catalyst after the OER was then detected. The results indicate that S-doped CoOOH/CuO nanosheets formed on the catalyst surface during the OER may act as the catalytic active substance. Furthermore, when employed as an air cathode in a Zn-air battery, it reveals a high open-cycle potential of 1.38 V and a peak power density of 123.9 mW cm-2. The performance of the rechargeable Zn-air battery is close to that fabricated with commercial precious metal-based electrocatalysts. These findings would furnish some guidelines for the design, development, and applications of bimetallic sulfide electrocatalysts for the OER.

Dual-Plasmonic Gold@Copper Sulfide Core-Shell Nanoparticles: Phase-Selective Synthesis and Multimodal Photothermal and Photocatalytic Behaviors.

Although the intriguing plasmonic properties of noble metal nanoparticles originate from the collective oscillations of free electrons in the conduction band, nanoparticles of doped semiconductors may also exhibit metal-like, plasmonic features that are dictated by the resonantly excited free hole oscillations in the valence band. Here, we combine Au, a representative free electron metal, with copper sulfides, a class of plasmonic p-type semiconductors, in a core-shell nanoparticle geometry to construct dual-plasmonic hetero-nanostructures displaying unique multiplex optical characteristics dominated by plasmonic hole oscillations in the semiconductor shells, plasmonic electron oscillations in the metallic cores, and interband electronic transitions from the valence to conduction bands. Through deliberately designed colloidal synthesis, we are able to selectively grow nanoshells comprising copper sulfides of specifically targeted crystalline phases and Cu/S stoichiometries, such as covellite (CuS), digenite (Cu1.8S), and nonstoichiometric Cu2-xS, on the surfaces of Au nanoparticle cores. Our synthetic approach enables us not only to finely control the core and shell dimensions but also to systematically adjust the free hole concentrations in the semiconductor shells, which forms the keystone for the fine tuning of multiple optical resonance modes supported by these hybrid hetero-nanostructures. The dual-plasmonic Au@copper sulfide core-shell nanoparticles exhibit unique multimodal photothermal and photocatalytic behaviors upon selective photoexcitations of different optical transitions at their characteristic resonant frequencies, allowing us to quantitatively evaluate and rigorously compare the intrinsic photothermal and photocatalytic efficacies of multiple types of hot charge carriers, all photoexcited in the same hybrid nanoparticles but with distinct photophysical origins, excited-state lifetimes, energy distributions, and transfer pathways.

Preparation of Biscuit-Like SO2-4/ZrO2 Catalyst for Alkylation of o-Xylene with Styrene.

We present here a facile synthesis of SO2-4/ZrO2 solid superacid by impregnating the biscuit-like mesoporous ZrO2 nanoparticles prepared by an emulsion combustion method directly into H2SO4 solution. The obtained solid acid catalyst was characterized by means of X-ray powder diffraction, transmission and scanning electron microscopy, thermogravimetry, Brunner-Emmet-Teller measurement, and infrared analysis. Its catalytic performance was examined by alkylation of o-xylene with styrene. The optimal catalytic formulation, obtained from the investigation of experimental conditions, was determined to be 5 wt% of catalyst loading with initial o-xylene/styrene molar ratio of 5 under reaction temperature at 120 °C for 120 min, achieving a 100% styrene conversion and a 93.3% 1-phenyl-1-xylyl ethane selectivity. The biscuit-like SO2-4/ZrO2 solid acid exhibited high catalytic activity and selectivity and excellent structural stability. This synthetic strategy for preparing the mesoporous SO2-4 promoted ZrO2 solid superacid catalyst is generalized and expected to be applied to other metal oxides.

Ammonium Nitrate-Assisted Synthesis of Nitrogen/Sulfur-Codoped Hierarchically Porous Carbons Derived from Ginkgo Leaf for Supercapacitors.

Biomass-derived carbons for supercapacitors provide a promising and sustainable strategy to address the worldwide energy and climate change challenges. Here, we have designed and constructed three-dimensional nitrogen/sulfur-codoped hierarchically porous carbons for high-performance supercapacitor electrode materials in a one-step process, in which ginkgo leaf is used as a carbon source and S source and ammonium nitrate (AN) is used as an activating agent and a N source. During the synchronous carbonization and activation process, AN could be decomposed completely into gaseous byproducts and be removed easily without leaving residues after product formation. The as-synthesized ginkgo leaf-derived carbons exhibited a high specific capacitance of 330.5 F g-1 at a current density of 0.5 A g-1 and a capacitance of 252 F g-1 even at a high current density of 10 A g-1 with an excellent capacitance retention of 85.8% after 10 000 cycles in 6 mol L-1 KOH electrolyte. The present study provides an efficient, sustainable, and facile approach to prepare renewable hierarchically porous carbons as advanced electrode materials for energy storage and conversion.

Hot carriers in action: multimodal photocatalysis on Au@SnO2 core-shell nanoparticles.

Metal-semiconductor hybrid heteronanostructures exhibit intriguing multimodal photocatalytic behaviors dictated by multiple types of photoexcited charge carriers with distinct energy distribution profiles, excited-state lifetimes, and interfacial transfer dynamics. Here we take full advantage of the optical tunability offered by Au@SnO2 core-shell nanoparticles to systematically tune the frequencies of plasmonic electron oscillations in the visible and near-infrared over a broad spectral range well-below the energy thresholds for the interband transitions of Au and the excitonic excitations of SnO2. Employing Au@SnO2 core-shell nanoparticles as an optically tunable photocatalyst, we have been able to create energetic hot carriers exploitable for photocatalysis by selectively exciting the plasmonic intraband transitions and the d → sp interband transitions in the Au cores at energies below the band gap of the SnO2 shells. Using photocatalytic mineralization of organic dye molecules as model reactions, we show that the interband and plasmonic intraband hot carriers exhibit drastically distinct photocatalytic behaviors in terms of charge transfer pathways, excitation power dependence, and apparent photonic efficiencies. The insights gained from this work form an important knowledge foundation guiding the rational optimization of hot carrier-driven chemical transformations on nanostructured metal-semiconductor hybrid photocatalysts.

Nanoscale Surface Curvature Effects on Ligand-Nanoparticle Interactions: A Plasmon-Enhanced Spectroscopic Study of Thiolated Ligand Adsorption, Desorption, and Exchange on Gold Nanoparticles.

The interfacial adsorption, desorption, and exchange behaviors of thiolated ligands on nanotextured Au nanoparticle surfaces exhibit phenomenal site-to-site variations essentially dictated by the local surface curvatures, resulting in heterogeneous thermodynamic and kinetic profiles remarkably more sophisticated than those associated with the self-assembly of organothiol ligand monolayers on atomically flat Au surfaces. Here we use plasmon-enhanced Raman scattering as a spectroscopic tool combining time-resolving and molecular fingerprinting capabilities to quantitatively correlate the ligand dynamics with detailed molecular structures in real time under a diverse set of ligand adsorption, desorption, and exchange conditions at both equilibrium and nonequilibrium states, which enables us to delineate the effects of nanoscale surface curvature on the binding affinity, cooperativity, structural ordering, and the adsorption/desorption/exchange kinetics of organothiol ligands on colloidal Au nanoparticles. This work provides mechanistic insights on the key thermodynamic, kinetic, and geometric factors underpinning the surface curvature-dependent interfacial ligand behaviors, which serve as a central knowledge framework guiding the site-selective incorporation of desired surface functionalities into individual metallic nanoparticles for specific applications.

Multifaceted Gold-Palladium Bimetallic Nanorods and Their Geometric, Compositional, and Catalytic Tunabilities.

Kinetically controlled, seed-mediated co-reduction provides a robust and versatile synthetic approach to multimetallic nanoparticles with precisely controlled geometries and compositions. Here, we demonstrate that single-crystalline cylindrical Au nanorods selectively transform into a series of structurally distinct Au@Au-Pd alloy core-shell bimetallic nanorods with exotic multifaceted geometries enclosed by specific types of facets upon seed-mediated Au-Pd co-reduction under diffusion-controlled conditions. By adjusting several key synthetic parameters, such as the Pd/Au precursor ratio, the reducing agent concentration, the capping surfactant concentration, and foreign metal ion additives, we have been able to simultaneously fine-tailor the atomic-level surface structures and fine-tune the compositional stoichiometries of the multifaceted Au-Pd bimetallic nanorods. Using the catalytic hydrogenation of 4-nitrophenol by ammonia borane as a model reaction obeying the Langmuir-Hinshelwood kinetics, we further show that the relative surface binding affinities of the reactants and the rates of interfacial charge transfers, both of which play key roles in determining the overall reaction kinetics, strongly depend upon the surface atomic coordinations and the compositional stoichiometries of the colloidal Au-Pd alloy nanocatalysts. The insights gained from this work not only shed light on the underlying mechanisms dictating the intriguing geometric evolution of multimetallic nanocrystals during seed-mediated co-reduction but also provide an important knowledge framework that guides the rational design of architecturally sophisticated multimetallic nanostructures toward optimization of catalytic molecular transformations.

Thermal stability and mechanism of decomposition of emulsion explosives in the presence of pyrite.

The reaction of emulsion explosives (ammonium nitrate) with pyrite was studied using techniques of TG-DTG-DTA. TG-DSC-MS was also used to analyze samples thermal decomposition process. When a mixture of pyrite and emulsion explosives was heated at a constant heating rate of 10K/min from room temperature to 350°C, exothermic reactions occurred at about 200°C. The essence of reaction between emulsion explosives and pyrite is the reaction between ammonium nitrate and pyrite. Emulsion explosives have excellent thermal stability but it does not mean it showed the same excellent thermal stability when pyrite was added. Package emulsion explosives were more suitable to use in pyrite shale than bulk emulsion explosives. The exothermic reaction was considered to take place between ammonium nitrate and pyrite where NO, NO2, NH3, SO2 and N2O gases were produced. Based on the analysis of the gaseous, a new overall reaction was proposed, which was thermodynamically favorable. The results have significant implication in the understanding of stability of emulsion explosives in reactive mining grounds containing pyrite minerals.

Quantum confinement effects on charge-transfer between PbS quantum dots and 4-mercaptopyridine.

We obtain the surface enhanced Raman spectra of 4-mercaptopyridine on lead sulfide (PbS) quantum dots as a function of nanoparticle size and excitation wavelength. The nanoparticle radii are selected to be less than the exciton Bohr radius of PbS, enabling the observation of quantum confinement effects on the spectrum. We utilize the variation of nontotally symmetric modes of both b(1) and b(2) symmetry as compared to the totally symmetric a(1) modes to measure the degree of charge-transfer between the molecule and quantum dot. We find both size dependent and wavelength dependent resonances in the range of these measurements, and attribute them to charge-transfer resonances which are responsible for the Raman enhancement.

Excitation profile of surface-enhanced Raman scattering in graphene-metal nanoparticle based derivatives.

Understanding energy transfer mechanisms in graphene derivatives is strongly motivated by the unusually interesting electronic properties of graphene, which can provide a template for the creation of novel nanostructured derivatives. From a synthetic point of view, it is highly attractive to envision being able to synthesize pristine graphene from precursors such as graphene oxide (GO). While this goal may be challenging over large length-scales, it is possible to generate regions of graphene at the nanoscale, confirmed by Raman spectroscopy or other methods. We describe an in situ method of nucleating gold or palladium nanoparticles in the presence of ethylene glycol as a reducing agent, while simultaneously reducing GO to graphene. The Au nanoparticles aid in spectroscopic characterization by both quenching fluorescence, allowing the graphene D and G bands to be quantified, and yielding a surface enhancement of about two orders of magnitude. We observe the excitation profile (488-785 nm) of the surface enhanced Raman spectrum (SERS) of graphene with Au nanoparticles adsorbed on the surface. Both the D and G bands display a resonance at approximately 593 nm (2.09 eV). This resonance may be interpreted as a combination of the plasmon resonance at 548 nm and a likely contribution from charge transfer as well. In addition, we observe a stiffening of the G band compared with that of graphene. The mechanism of the SERS, whether plasmonic or charge transfer-based, enables insight into the electronic pathways available to the graphene-nanoparticle system. We discuss our results in the context of several existing studies of graphene-based nanostructure derivatives.