Dispersion of Active Au Nanoparticles on Mesoporous SBA-15 Materials

Chemical modification(CM)and deposition-precipitation(DP)methods were used for the dispersion of active Au nanoparticles on mesoporous silica materials in this work.XRD,TEM,N2 adsorption isotherms and UV-Vis absorption spectra were used to characterize in detail Au-SBA-15 materials prepared by the two methods. The analysis results showed that high loading(1.7%,by mass)and uniform Au nanoparticles(approximately 3 nm) were dispersed in the channels of mesoporous SBA-15 by the CM method.While for the DP method,most of Au nanoparticles with the size of 10—15nm were aggregated outside of the channels of SBA-15 and the actual loading of Au was only 0.38%(by mass).

Tailoring the surface structures of iron oxide nanorods to support Au nanoparticles for CO oxidation

Iron oxide supported Au nanomaterials are one of the most studied catalysts for low-temperature CO oxidation.Catalytic performance not only critically depends on the size of the supported Au nanoparticles(NPs)but also strongly on the chemical nature of the iron oxide.In this study,Au NPs supported on iron oxide nanorods with different surface properties throughβ-FeOOH annealing,at varying temperatures,were synthesized,and applied in the CO oxidation.Detailed characterizations of the interactions between Au NPs and iron oxides were obtained by X-ray diffraction,transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy.The results indicate that the surface hydroxyl group on the Au/FeOOH catalyst,before calcination(Au/FeOOH-fresh),could facilitate the oxygen adsorption and dissociation on positively charged Au,thereby contributing to the low-temperature CO oxidation reactivity.After calcination at 200℃,under air exposure,the chemical state of the supported Au NP on varied iron oxides partly changed from metal cation to Au0,along with the disappearance of the surface OH species.Au/FeOOH with the highest Au0 content exhibits the highest activity in CO oxidation,among the as-synthesized catalysts.Furthermore,good durability in CO oxidation was achieved over the Au/FeOOH catalyst for 12 h without observable deactivation.In addition,the advanced identical-location TEM method was applied to the gas phase reaction to probe the structure evolution of the Au/iron oxide series of the catalysts and support structure.A Au NP size-dependent Ostwald ripening process mediated by the transport of Au(CO)x mobile species under certain reaction conditions is proposed,which offers a new insight into the validity of the structure-performance relationship.

Improved Plasmonic Hot‑Electron Capture in Au Nanoparticle/Polymeric Carbon Nitride by Pt Single Atoms for Broad‑Spectrum Photocatalytic H_(2)Evolution

ABSTRACT Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a“holy grail”for researchers,but is still a challenging issue.Herein,based on the common polymeric carbon nitride(PCN),a hybrid co-catalysts system comprising plasmonic Au nanoparticles(NPs)and atomically dispersed Pt single atoms(PtSAs)with different functions was constructed to address this challenge.For the dual co-catalysts decorated PCN(PtSAs–Au_(2.5)/PCN),the PCN is photoexcited to generate electrons under UV and short-wavelength visible light,and the synergetic Au NPs and PtSAs not only accelerate charge separation and transfer though Schottky junctions and metal-support bond but also act as the co-catalysts for H_(2) evolution.Furthermore,the Au NPs absorb long-wavelength visible light owing to its localized surface plasmon resonance,and the adjacent PtSAs trap the plasmonic hot-electrons for H_(2) evolution via direct electron transfer effect.Consequently,the PtSAs–Au_(2.5)/PCN exhibits excellent broad-spectrum photocatalytic H_(2) evolution activity with the H_(2) evolution rate of 8.8 mmol g^(−1) h^(−1) at 420 nm and 264μmol g^(−1) h^(−1) at 550 nm,much higher than that of Au_(2.5)/PCN and PtSAs–PCN,respectively.This work provides a new strategy to design broad-spectrum photocatalysts for energy conversion reaction.

Novel Au nanoparticles-inlaid titanium paper for PEM water electrolysis with enhanced interfacial electrical conductivity

Proton-exchange membrane water electrolysis(PEM WE)is a particularly promising technology for renewable hydrogen produc-tion.However,the excessive passivation of the gas diffusion layer(GDL)will seriously affect the high surface-contact resistance and result in energy losses.Thus,a mechanism for improving the conductivity and interface stability of the GDL is an urgent issue.In this work,we have prepared a hydrophilic and corrosion resistant conductive composite protective coating.The polydopamine(PDA)film on the Ti surface,which was obtained via the solution oxidation method,ensured that neither micropores nor pinholes existed in the final hybrid coatings.In-situ reduced gold nanoparticles(AuNPs)improved the conductivity to achieve the desired interfacial contact resistance and further enhanced the corrosion resistance.The surface composition of the treated samples was investigated using scanning electron microscopy(SEM),transmis-sion electron microscopy(TEM),X-ray diffraction(XRD),and Fourier transform infrared spectroscopy(FTIR).The results indicated that the optimized reaction conditions included a pH value of 3 of HAuCl_(4) solution with PDA deposition(48 h)on papers and revealed the lowest con-tact resistance(0.5 mΩ·cm^(2))and corrosion resistance(0.001μA·cm^(−2))in a 0.5 M H_(2)SO_(4)+2 ppm F−solution(1.7 V vs.RHE)among all the modified specimens,where RHE represents reversible hydrogen electrode.These findings indicated that the Au-PDA coating is very appropriate for the modification of Ti GDLs in PEM WE systems.

Transient competition between photocatalysis and carrier recombination in TiO_2 nanotube film loaded with Au nanoparticles

Highly ordered TiO2 nanotube array （TNA） films are fabricated by using an anodic oxidation method. Au nanoparticles （NPs） films are decorated onto the top of TNA films with the aid of ion-sputtering and thermal annealing. An enhanced photocatalytic activity under ultraviolet C （UVC, 266 nm） light irradiation is obtained compared with that of the pristine TNA, which is shown by the steady-state photoluminescence （PL） spectra. Furthermore, a distinct blue shift in the nanosecond time-resolved transient photoluminescence （NTRT-PL） spectra is observed. Such a phenomenon could be well explained by considering the competition between the surface photocatalytic process and the recombination of the photo-generated carriers. The enhanced UV photocatalytic activities of the Au-TNA composite are evaluated through photo-degradation of methyl orange （MO） in an aqueous solution with ultraviolet-visible absorption spectrometry. Our current work may provide a simple strategy to synthesize defect-related composite photocatalytic devices.

Study on the Electrical Conductivity of Au Nanoparticle/Chloroform and Toluene Suspensions

Au nanoparticles capped by hexadecanethiol and dodecanethiol were chemically synthesized. The characteristics of electrical conductivity for the capped nanoparticles dissolved in chloroform and toluene solvents were investigated. The electrical conductivity of the samples is conspicuously Au nanoparticle concentration dependent. The results show that a rapid conductivity increases when the nanoparticle concentration increases from low value to a moderate value of 5.47 g/L and 11.22 g/L, which is capped by hexadecanethiol and dodecanethiol in chloroform solvent, and 2.77 g/L and 7.88 g/L in toluene solvent. The room-temperature dc conductivity σ dc of Au nanoparticle capped by hexadecanethiol is smaller than that capped by dodecanethiol in the whole range of Au nanoparticle concentrations. The conductivity of Au nanoparticle suspensions increases almost linearly in the temperature range in above two solvents.

The enhancement of 21.2%-power conversion efficiency in polymer photovoltaic cells by using mixed Au nanoparticles with a wide absorption spectrum of 400 nm–1000 nm

Au nanoparticles （NPs） mixed with a majority of bone-like, rod, and cube shapes and a minority of irregu- lar spheres, which can generate a wide absorption spectrum of 400 nm-1000 nm and three localized surface plas- mon resonance peaks, respectively, at 525, 575, and 775 nrn, are introduced into the hole extraction layer poly（3,4- ethylenedioxythiophene）：poly（4-styrenesulfonate） （PEDOT：PSS） to improve optical-to-electrical conversion performances in polymer photovoltaic ceils. With the doping concentration of Au NPs optimized, the cell performance is significantly improved： the short-circuit current density and power conversion efficiency of the poly（3-hexylthiophene）： [6,6]-phenyl- C60-butyric acid methyl ester cell are increased by 20.54% and 21.2%, reaching 11.15 mA.cm-2 and 4.23%. The variations of optical, electrical, and morphology with the incorporation of Au NPs in the cells are analyzed in detail, and our results demonstrate that the cell performance improvement can be attributed to a synergistic reaction, including： 1） both the local- ized surface plasmon resonanceand scattering-induced absorption enhancement of the active layer, 2） Au doping-induced hole transport/extraction ability enhancement, and 3） large interface roughness-induced efficient exciton dissociation and hole collection.

Microwave Synthesis of Au Nanoparticles with the System of AuCl_4-CH_3CH_2OH

The Au nanoparticles has been prepared by microwave high-pressure procedure with alcohol as the reducing agent. The color of colloidal Au nanoparticles is blue-violet. The maximum absorption spectrum of colloidal Au is at 580 nm, and the resonance scattering peak is at 580 nm. Using this method, the colloidal Au of long-time stability can be prepared Simply and quickly.

Preparation and Catalytic Performance of Microporous Polymer/Au Nanoparticles Composite Microspheres

Polystyrene crosslinked microspheres were prepared by soap-free emulsion polymerization using styrene (St) and divinylbenzene (DVB) as monomers;then,the microporous structure was knitted by the Friedel-Crafts alkylation reaction,and the Au nanoparticles (AuNPs) were loaded into the pores through thermal reduction,to obtain AuNPs/ hyper-crosslinked microporous polymer composite microspheres.SEM and particle-size test results show that the microspheres show good monodispersity.The micropore analysis indicates that the specific surface area and the pore volume of the microporous polymer microspheres decrease with increasing DVB content,and when the DVB content is 0.1%,the specific surface area reaches a maximum of 1 174.6 m2/g.After loading AuNPs,the specific surface area and the amount of micropores of the composite microspheres decrease obviously.The results of XRD and XPS analyses suggest that HAuCl4 is reduced to AuNPs.The composite microspheres show a good catalytic performance for the reduction catalyst of 4-nitrophenol.

Highly Sensitive SnO_2 Nanorods Ethanol Sensors with the Adsorption of Au Nanoparticles

Flower-liked SnO_2 nanorods were prepared by a hydrothermal method.The sensors were fabricated using SnO_2 nanorods adsorption of Au nanoparticles through sputtering deposition.We found that the loading of a small amount of Au nanoparticles on the surface of SnO_2 nanorods can effectively enhance and functionalize the gas sensing performance of SnO_2 nanorods,which due to the Au adsorption make the surface-depletion effect more pronounced.Such enhanced surface depletion increases the sensitivity,lowers the operation temperature and decreases the response time.

Engineering Shewanella-re duce d graphene oxide aerogel biohybrid to efficiently synthesize Au nanoparticles

Biosynthesizing Au nanoparticles(AuNPs)from gold-bearing scraps provides a sustainable method to meet the urgent demand for AuNPs.However,it remains challenging to efficiently biosynthesize AuNPs of which the diameter is less than 10 nm from a trace amount of Au^(3+)concentration at the level of tens ppm.Here,we constructed an exoelectrogenic cell(eCell)-conductive reduced-graphene-oxide aero-gel(rGA)biohybrid by assembling Shewanella sp.S1(SS1)as living biocatalyst and rGA as conductive ad-sorbent,in which Au^(3+)at trace concentrations would be enriched by the adsorption of rGA and reduced to AuNPs through the extracellular electron transfer(EET)of SS1.To regulate the size of the synthe-sized AuNPs to 10 nm,the strain SS1 was engineered to enhance its EET,resulting in strain RS2(pYYD-P tac-ribADEHC&pHG13-P_(bad)-omcC in SS1).Strain RS2 was further assembled with rGA to construct the RS2-rGA biohybrid,which could synthesize AuNPs with the size of 7.62±2.82 nm from 60 ppm Au^(3+)so-lution.The eCell-rGA biohybrid integrated Au^(3+)adsorption and reduction,which enabled AuNPs biosyn-thesis from a trace amount of Au^(3+).Thus,the required Au^(3+)ions concentration was reduced by one or two orders of magnitude compared with conventional methods of AuNPs biosynthesis.Our work devel-oped an AuNPs size regulation technology via engineering eCell’s EET with synthetic biology methods,providing a feasible approach to synthesize AuNPs with controllable size from trace level of gold ions.

Predesigned covalent organic framework with sulfur coordination: Anchoring Au nanoparticles for sensitive colorimetric detection of Hg(Ⅱ)

Targeted construction of new covalent organic frameworks(COFs)with specific purposes and rationalities to build colorimetric assay platform for environmental pollutant monitoring have attracted increasing interest.However,it is still challenging due to lack of available coordination sites inside COFs pores and only a slight bonding ability for anchoring metal.In this work,a two-dimensional(2D)COFs(termed as Tz-COF)with high crystallinity,excellent chemical stability,and abundant sulfur coordination in its skeletons was synthesized and used for the confined growth of Au NPs.It was found that the Au NPs showed significant dispersibility for the support of Tz-COF.The proposed Tz-COF@Au NPs possessed outstanding Hg^(2+)-activated peroxidase-like activity benefited from physicochemical properties of gold amalgam and synergistic effect between COFs and Au NPs to oxidize chromogenic substrate.Based on highly efficient activity and distinctive color evolution,the strategy for detecting Hg^(2+)was developed and successfully applied to determine the content of Hg^(2+)in real environmental samples.This work manifests that a potential strategy to establish a colorimetric assay platform for environmental pollutant monitoring based on the targeted manufacturing of novel COFs with specific functions.

A Facile Synthesis of Monodisperse Au Nanoparticles and Their Catalysis of CO Oxidation

Monodisperse Au nanoparticles(NPs)have been synthesized at room temperature via a burst nucleation of Au upon injection of the reducing agent t-butylamine-borane complex into a 1,2,3,4-tetrahydronaphthalene solution of HAuCl4·3H2O in the presence of oleylamine.The as-synthesized Au NPs show size-dependent surface plasmonic properties between 520 and 530 nm.They adopt an icosahedral shape and are polycrystalline with multiple-twinned structures.When deposited on a graphitized porous carbon support,the NPs are highly active for CO oxidation,showing 100%CO conversion at-45°C.

Plasmonic Au nanoparticles supported on both sides of Ti02 hollow spheres for maximising photocatalytic activity under visible light

A strategy of intensifying the visible light harvesting ability of anatase Ti02 hollow spheres(HSs)was developed,in which both sides of Ti02 HSs were utilised for stabilising Au nanoparticles(NPs)through the sacrificial templating method and convex surface-induced confinement.The composite structure of single Au NP yolk-Ti02 shell-Au NPs,denoted as Au@Au(Ti02,was rendered and confirmed by the transmission electron microscopy analysis.Au@Au(Ti02 showed enhanced photocatalytic activity in the degradation of methylene blue and phenol in aqueous phase under visible light surpassing that of other reference materials such as Au(Ti02 by 77%and Au@P25 by 52%,respectively,in phenol degradation.

Sodium Citrate： A Universal Reducing Agent for Reduction/ Decoration of Graphene Oxide with Au Nanoparticles

A facile method is proposed for the synthesis of reduced graphene oxide nanosheets （RGONS） and Au nanoparticle-reduced graphene oxide nanosheet （Au-RGONS） hybrid materials, using graphene oxide （GO） as precursor and sodium citrate as reductant and stabilizer. The resulting RGONS and Au-RGONS hybrid materials were characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, atomic force microscopy, transmission electron microscopy, and X-ray diffraction. It was found that the RGONS and Au-RGONS hybrid materials formed stable colloidal dispersions through hydrogen bonds between the residual oxygen-containing functionalities on the surface of RGONS and the hydroxyl/carboxyl groups of sodium citrate. The electrochemical responses of RGONS and Au-RGONS hybrid material-modified glassy carbon electrodes （GCE） to three kinds of biomolecules were investigated, and all of them showed a remarkable increase in electrochemical performance relative to a bare GCE.

Fluorescence enhancement of acridine orange in a water solution by Au nanoparticles

The surface enhanced fluorescence effect of acridine orange fluorophore in the proximity of Au nanoparticles has been investigated experimentally in the system of aqueous solution.Significant enhancement of the fluorescence intensity was observed when the system was excited with 532 nm or 442 nm CW lasers.The influence of the distances between neighboring Au particles as well as that between the fluorophore molecules and the Au surface were explored experimentally.The results demonstrated that a compact distribution of metallic particles was able to produce stronger fluorescence enhancement.Proper separation between the fluorophore molecules and the metal surface was favorable for a better enhancement.

Green-chemistry Compatible Approach to TiO_2-supported PdAu Bimetallic Nanoparticles for Solvent-free 1-Phenylethanol Oxidation under Mild Conditions

Ti O2-supported Pd Au bimetallic nanoparticles(NPs) with small size and good dispersity were prepared by the room-temperature ionic liquid-assisted bimetal sputtering, which is simple, environmentally friendly, and free of additives and byproducts. Pd/Au atomic ratio can be tuned by controlling the sputtering conditions simply. High catalytic activity was found in Pd Au–NPs–Ti O2 hybrids for solvent-free selective oxidation of 1-phenylethanol using O2 as the oxidant at the low temperature of 50 °C and low pressure of 1 atm. It was found that Pd/Au ratio strongly affected the catalytical activity, and the highest conversion of about 35 % and turnover frequency of about 421 h-1were achieved at 1:1 of Pd/Au atomic ratio. The synergistic effect in Pd Au NPs was also discussed based on the comprehensive characterization results.The present approach may offer an alternative platform for future development of green-chemistry compatible bimetallic nanocatalysts.

Microwave-assisted synthesis of ultrafine Au nanoparticles immobilized on MOF-199 in high loading as efficient catalysts for a three-component coupling reaction

Controlled integration of ultrafine metal nanoparticles （MNPs） and metal- organic frameworks （MOFs） has drawn much attention due to their unique physical and chemical properties. However, the development of a one-step strategy for preparing ultrafine MNPs within MOFs still remains a great challenge. Herein, a facile synthetic approach toward the abovementioned composites was developed. In contrast to the conventional approach, these hybrids were prepared by the direct mixing of metal and MOF precursors in the reaction solution assisted by microwave irradiation. Impressively, the Au/MOF-199 composite with uniformly distributed ultrafine Au nanoparticles could be fabricated in only two minutes, and the Au loading could be increased up to a level of 5.13%. The multifunctional Au/MOF-199 catalysts exhibited high turnover numbers （TONs） and turnover frequencies （TOFs） in the three-component coupling reaction of formaldehyde, phenylacetylene, and piperidine （AB-coupling）. Owing to the confinement effect of MOF-199, the 5.13%Au/MOF-199 catalyst could be recycled for five runs without serious loss of activity, with no obvious aggregation of Au NPs detected.

Determination of Hydrocortisone in Cosmetics by CdSe/CdS Quantum Dots-Based Fluoroimmunoassay Using Magnetic Fe304/Au Nanoparticles as Solid Carriers

This work demonstrated the feasibility of detecting hydrocortisone in cosmetics using a novel CdSe/CdS quan- tum dots-based competitive fluoroimmunoassay with magnetic core/shell Fe3Oa/Au nanoparticles （MCFN） as solid carriers. Hydrocortisone antigen was labeled with the synthesized core/shell CdSe/CdS quantum dots （QDs） to form the antigen-QDs conjugate. Meanwhile, hydrocortisone antibody was incubated with MCFN and the immobilized antibody was obtained. The immobilized antibody was then mixed sequentially with hydrocortisone and a slightly excess amount of the QDs-labeled hydrocortisone antigen, allowing their competition for binding with the antibody immobilized on MCFN. The bound hydrocortisone and the antigen-QDs conjugates on MCFN were removed subsequently after the mixture was applied to a magnetic force. The analyte concentration was obtained by measuring the fluorescence intensity of the unbound hydrocortisone antigen-QDs conjugates. The proposed method was characterized by simplicity, rapidity, and high sensitivity with a wide linear working range of 0.5 to 15000 pg·mL^-1 and a low detection limit of 0.5 pg.mL^- 1. The proposed method was successfully applied to the determination of hydrocortisone in cosmetics with satisfactory results.

Electroless deposition of Au nanoparticles on reduced graphene oxide/polyimide film for electrochemical detection of hydroquinone and catechol

An electrochemical sensor for determination of hydroquinone （HQ） and catechol （CC） was developed using Au nanoparticles （AuNPs） fabricated on reduced graphene oxide/polyimide （PIIRGO） film by electroless deposition. The electrochemical behaviors of HQ and CC at PIIRGO-AuNPs electrode were investigated by cyclic voltammetry （CV） and differential pulse voltammetry （DPV）. Under the optimized condition, the current responses at PI/RGO-AuNPs electrode were linear over ranges from 1 to 654 mol/L for HQ and from 2 to 1289 mol/L for CC, with the detection limits of 0.09 and 0.2 mollL, respectively. The proposed electrode exhibited good reproducibility, stability and selectivity. In addition, the proposed electrode was successfully applied in the determination of HQ and CC in tap water and the Yellow River samples.