Au Particles Research Articles

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters

AbstractThe selective synthesis of valuable azo‐ and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine‐tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF‐8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs) selectively catalyzed nitrobenzene reduction to azobenzene. X‐ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO‐DRIFTS) of Au NC/ZIF‐8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF‐8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF‐8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure‐selectivity relationships.

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters.

The selective synthesis of valuable azo- and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine-tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF-8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs) selectively catalyzed nitrobenzene reduction to azobenzene. X-ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO-DRIFTS) of Au NC/ZIF-8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF-8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF-8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure-selectivity relationships.

Nano-sized gold particles driven interfacial reaction for the enhanced electrochemical nitrite sensing

Nitrite is a typical food additive and chemical fertilizer, which could pose toxicity to human and aquatic organisms when it is excessive. Therefore, it is meaningful to develop reliable analytical methods for nitrite detection. In this work, an innovative electrochemical nitrite sensor has been fabricated using In2O3 decorated with high-activity nano-sized Au particles (Au/In2O3), which were synthesized through a two-step synthetic method combining hydrothermal reaction and deposition-precipitation, resulting in an excellent sensing performance for the nitrite. Specifically, the electrochemical nitrite sensor based on Au/In2O3 exhibits high sensitivity with a linear detection range from 10 μM to 5 mM at pH 7.38. Additionally, the Au/In2O3 based nitrite sensor shows a detection limit of 0.46 μM and presents impressive selectivity and stability. The extraordinary nitrite sensing performance can be attributed to the excellent catalytic activity of nano-sized Au particles and the strong interfacial reaction between Au/In2O3 and nitrite. Furthermore, theoretical calculations reveal the interfacial reactions mechanism driven by Au particles, which enhance the charge transfer between Au/In2O3 and nitrite and thus improve its electrochemical sensing performance. This work presents a novel approach towards fabricating high-performance electrochemical nitrite sensor and reveals the enhanced interfacial reaction mechanism of nano-sized Au particles.

Supported Binuclear Gold Phosphine Complexes as CO Oxidation Catalysts: Insights into the Formation of Surface‐Stabilized Au Particles

Atomically precise gold phosphine complexes as precursors for supported Au catalysts tested in CO oxidation are presented. Using a variety of analytical techniques, including in situ and operando X‐ray absorption spectroscopy, it is discovered that minor changes in the ligand of the molecular complexes result in significantly different activation behaviors of supported Au catalysts under reaction conditions. When using [Au2(μ2‐POP)2]OTf2 (POP = tetraphenylphosphoxane) as single‐source precursor, an active supported oxidation catalyst in second light‐off is obtained, outperforming a commercial Au/TiO2 and a P‐free Au/Al2O3 reference catalyst. Conversely, using [Au2(μ2‐dppe)2]OTf2 (dppe = diphenylphosphinoethane) on alumina leads to a significant decrease in CO oxidation activity. This difference is attributed to the formation of P‐containing ligand residues on the support in the case of [Au2(μ2‐POP)2]OTf2/Al2O3, which enhances the thermal stability of the Au particles and affects the particle's electronic properties through charge transfer processes. This work provides insights into the dynamic ligand decomposition of molecular gold complexes under reaction conditions and demonstrates the delicate balance between the stabilization of Au particles, clusters, and complexes using ligands and the blocking of active sites. This knowledge will pave the way for the targeted use of molecular transition metal complexes as precursors in synthesizing surface‐stabilized nanoparticles.

Parkinson biomarker determination with an Au microflower-enhanced electrochemical immunosensor using non-Faradaic capacitancemeasurements.

This work comprehends the development and characterization of a carbon black-based electrode modified with Au microflowers to increase its effect as a capacitance biosensor for the determination of PARK7/DJ-1. Due to its high surface-to-volume ratio and biocompatibility, Au particles are suitable for antibody binding, and by monitoring surface capacitance, it is possible to identify the immune-pair interaction. Au microflowers allowed the adequate immobilization of Parkinsonian-related proteins: PARK7/DJ-1 and its antibody. The protein is associated with several antioxidant mechanisms, but its abnormal concentrations or mutations can be the cause of the loss of dopaminergic neurons, leading to Parkinson's disease. The device was characterized by scanning electron microscopy and cyclic voltammetry, revealing the flower-like structures and the electrochemically-interest enhancements they provide, such as increased heterogeneous electron transfer rate coefficient and electroactive area. The self-assembled monolayers of different molecules were optimized with the aid of 22 central composite experiments and a linear calibration curve was obtained between 0.700 and 120ngmL-1 of PARK7/DJ-1, with a limit of detection of 0.207ngmL-1. The data confirms that the addition of Au microflowers enhanced the electrochemical signal of the device, as well as allowed for the determination of an early stage Parkinson's disease biomarker with appreciable analytical performance.

Enhancement of visible light adsorption and photocatalytic degradation activity of organic dye by coating semiconducting TiO2 shell on plasmonic Au particles

The plasmonic effect enhances light absorption in semiconductor photocatalysts, while the noble metal-semiconductor interface promotes charge carrier transfer and separation, boosting photocatalytic activity. However, current methods for synthesizing metal-core TiO2-shell nanoparticles face challenges, such as keeping stable and preventing aggregation. This study presents a simple and moderate synthesis method for Au@TiO2 core-shell nanoparticles, enabling precise control over the TiO2 shell thickness and stable photocatalytic performance. Various characterization techniques were employed to assess the optical and structural properties of the synthesized Au@TiO2 core-shell nanostructures. The results demonstrated that increasing the Au core concentration led to a gradual decrease in TiO2 shell thickness. The adsorption properties and photocatalytic degradation efficiency of the synthesized Au@TiO2 core-shell nanostructured catalysts were thoroughly examined, particularly focusing on their performance with methyl orange (MO) and methylene blue (MB). Au@TiO2 achieved excellent adsorption performance for MO, with a maximum capacity of 231±6 mg/g. Furthermore, Au@TiO2 exhibited higher photocatalytic degradation activity of both MO and MB than pure TiO2. The mechanism study indicated that it attributed to enhanced visible light absorption, reduced bandgap, and higher valence band energy. Additionally, the Au@TiO2 catalysts showed good cyclic stability, making them promising for future applications. This research offers insights into designing efficient photocatalysts, addressing existing synthesis challenges, and contributing valuable references for future advancements.

High Temperature, Isothermal Growth Promotes Close Packing and Thermal Stability in DNA-Engineered Colloidal Crystals.

We report a strategy to accelerate the synthesis and increase the crystallinity of colloidal crystals (CCs) engineered with DNA. Specifically, by holding the DNA-modified Au particle building blocks above the Tm of the DNA bonding elements (i.e., free from the particles), but slightly below the Tm of the anticipated CC during the assembly process, crystallinity is increased, and enthalpically favored phases with high degrees of facet registration are observed. We studied the utility of this approach with systems for which the commonly adopted slow-cooling approach yielded primarily amorphous aggregates. In particular, we used it to synthesize high-volume fraction CCs from large (80 nm) anisotropic nanoparticles (cubes and rhombic dodecahedra) with short (<14 nm) DNA designed to restrict the degrees of freedom for the DNA bonds and maintain the anisotropy of the particle building block. Small-angle X-ray scattering and electron microscopy studies show that the crystalline phases synthesized via this method are more thermally stable than their corresponding aggregate phases, likely due to an increased number of DNA-DNA bonds between particles. Crystal size tunability (between 0.5 and 15 μm edge lengths) and epitaxial growth were demonstrated using this strategy by modulating the NaCl concentration in tandem with previously synthesized CC nuclei. Taken together, this isothermal strategy demonstrates how to deliberately crystallize a wide variety of anisotropic colloidal materials and expands the phase space accessible to nanoparticles modified with DNA.

Study on the controlled preparation of ZnO/CdS and its photocatalytic performance enhanced by Au particles

Study on the controlled preparation of ZnO/CdS and its photocatalytic performance enhanced by Au particles

Stepwise oxidation of refractory pyrite using persulfate for efficient leaching of gold and silver by an eco-friendly copper(II)-glycine-thiosulfate system

Chemical oxidation is a promising pretreatment method for refractory pyrite enclosure to enhance Au/Ag extraction. Here, persulfate was employed for stepwise oxidation of a refractory pyrite concentrate with encapsulated Au/Ag: (i) pyrite oxidation began with heating-activation persulfate, where hydroxyl radical (•OH) acted as the primary oxidative species for fast-dissolving pyrite into Fe ions; (ii) pyrite self-dissolved Fe ions were in-suit used as a moderate activator of persulfate to generate •OH for sustainable oxidizing pyrite at room temperature. Mineralogical studies have confirmed that oxidation of the sulfide enclosure (FeS2) significantly reduced the particle size of pyrite, accompanied by pores creation and an increase in specific surface area. The variation of microstructure liberated Au and Ag particles to lixiviants for extraction, significantly improving leaching efficiency in an eco-friendly copper(II)-glycine-thiosulfate system to 92.2 % for Au and 88.6 % for Ag, respectively. This work provides a promising process for separating precious metals from refractory pyrite.

Intensified O2 activation and lattice O supply at inverse oxide-metal interface for catalytic oxidation reactions: A case study in alcohol oxidation

Inverse oxide/metal catalysts are recently employed and of great importance in catalytic oxidation reactions, due to the high activity and sintering-resistance. However, the investigations for identification of active-site structure, adsorption-activation of O2, and insight into interface-enhanced mechanism are relatively scare. Herein, the inverse “CoOx-Au” ensemble (∼10 nm CoOx nanoparticles onto ∼30 nm Au particles) for gas-phase alcohol oxidation was exampled to investigate above issues, under the premise of delivering 92 % benzyl alcohol conversion with 98 % benzaldehyde selectivity at 240 °C and atmospheric pressure. It is revealed that O2 is activated at CoOx-Au interface. The “CoO-Au ↔ Co3O4-Au” redox cycle at CoOx-Au interface proceeds over the “CoO↔Co3O4” cycle on CoOx surface, due to the weakened interfacial Co-O bond. And the enhanced redox cycle intensifies O2 activation and lattice O supply. The O2 activation at inverse oxide-metal interface provides promising clue for rational design of inverse catalysts for catalytic oxidation reactions.

Disposable and flexible screen-printed-carbon electrode modified with Au/poly-beta-cyclodextrin as electrochemical platform for estriol detection

In this work, a screen-printed carbon electrode in polyethylene (SPPE) modified with Au particles and poly-beta-cyclodextrin polymeric film (SPPE/Au/p-beta-CD) was develop as an electrochemical platform to detect estriol (E3) in environmental and biological samples. The stability, reproducibility and sensitivity of the electrode were confirmed via physicochemical and electrochemical characterization. Electrochemical tests demonstrated an increase in the SPPE electroactive area when 70% graphite ink was applied, and transmission electron microscopy revealed an increase in surface complexity compared with that of the unmodified electrode. The electrochemical impedance spectroscopy (EIS) to SPPE/Au/p-beta-CD data indicated a decrease and increase in the Rct (0.096 kΩ cm2) and constant phase element (CPE) (28.34 µF cm−2) values, respectively. The analytical curve was plotted using concentrations ranging from 2.0 to 48.5 µmol/L and the best results were obtained at pH 4.0; a limit of detection (LD) of 1.88 µmol/L was obtained. During a study of interferents, the platform exhibited high selectivity for E3. The SPPE/Au/p-beta-CD exhibited recovery percentages of E3 between 100.32–110.17% in river water, and female urine, saliva, and sweat. The SPPE/Au/p-beta-CD as electrochemical platform proved to be a reproducible, selective, and low-cost sensor for the detection of E3 in different complex matrices. The modification of SPPE with Au and the beta-CD polymer made the electrode more sensitive and the method used is viable for real application.

Au@CuS Nanoshells for Surface-Enhanced Raman Scattering Image-Guided Tumor Photothermal Therapy with Accelerated Hepatobiliary Excretion.

Gold-based nanoparticles for surface-enhanced Raman scattering (SERS) imaging show great potential for precise tumor detection and photothermal therapy (PTT). However, the metabolizability of gold nanoparticles (Au NPs) raises big concerns. Herein, we designed a core-shelled nanostructure of copper sulfide (CuS)-coated Au NPs with surface pegylation (PEG-Au@CuS NSs). The excreted Au in the gallbladders at 1 h and 4 h in mice injected with PEG-Au@CuS NSs was 8.2- and 19.1-fold of that with the pegylated Au NPs (PEG-AuNPs) of the same Au particle size, respectively. By loading the Raman reporter 3,3'-Diethylthiatricarbocyanine iodide (DTTC) in the core-shell junction of PEG-Au@CuS NSs, the PEG-Au-DTTC@CuS NSs exhibited the Raman signal-to-noise (S/N) ratio of 4.01 after 24 h of intravenous (IV) injection in the mice bearing an orthotopic CT26-Luc colon tumor. By contrast, the DTTC-coated PEG-AuNPs (PEG-Au-DTTC NPs) achieved an S/N ratio of 2.71. Moreover, PEG-Au-DTTC@CuS NSs exhibited an increased photothermal conversion effect compared with PEG-Au-DTTC NPs excited with an 808-nm laser. PEG-Au-DTTC@CuS NSs enabled intraoperative SERS image-guided photothermal therapy for a complete cure of the colon tumor-bearing mice. Our data demonstrated that the PEG-Au-DTTC@CuS NSs are promising intraoperative Raman image-guided theranostic nanoplatform with enhanced hepatobiliary excretion.

(Invited) Plasmonic Yolk@Shell Nanocrystals for Photocatalytic Hydrogen Production

Plasmonic photocatalysts have garnered significant attention for hydrogen production due to their unique properties and efficiency in harnessing solar energy. This work is designed to develop yolk@shell nanocrystals as a high-efficiency photocatalyst model. The core yolk is composed of Au nanoparticles, and the shell is composed of hollow non-stoichiometric semiconductors. The compositional defects can induce a large number of free carriers, making non-stoichiometric semiconductors behave like noble metals and exhibit surface plasmon resonance (SPR) absorption. For yolk@shell nanocrystals, the core Au particles can move freely, which can effectively stir the surrounding reaction solution to increase the reaction rate. The confined space between the core particle and the shell layer can function as a nanoreactor to promote species diffusion to enhance catalysis kinetics. In addition, the core Au particles and the shell semiconductor can form metal/semiconductor heterojunction so as to exhibit remarkable photocatalytic performance. Several representative works from our lab will be introduced to demonstrate the promising potentials of plasmonic yolk@shell nanocrystals for hydrogen production applications.

Bonding Strength Evaluation of Sub-Micron Au Particle Bumps for High Density Packaging

Bonding Strength Evaluation of Sub-Micron Au Particle Bumps for High Density Packaging

Evaluating the selectivity of CO2 reduction reaction on elementary metal particles with DFT calculations

Electrocatalytic CO2 reduction reaction (CO2RR) towards two-electron products is a competent technique to convert renewable electricity into chemical energy at ambient conditions. Poly-crystalline metals are well-known electrocatalysts for CO2RR. However, no theoretical research was reported to date that evaluates the selectivity of two-electron CO2RR on metal particles. In this work, we proposed a paradigm to evaluate the product selectivity of CO2RR on metal particles. The product selectivity on three low-index surfaces of six metals (In, Pb, Ag, Au, Ni, and Pt) was firstly determined based on the detailed reaction mechanisms established for CO2RR to products of HCOOH and CO. Then, the product selectivity of CO2RR on the first four metal particles was evaluated using the effective free energy barrier which accounts for the facet dependence of CO2RR on the metal particles. The computational results well rationalize the experimental observations, namely preference of HCOOH to CO on the In and Pb particles with higher HCOOH selectivity on the Pb particle, while CO preferred to HCOOH on the Ag and Au particles with higher CO selectivity on the Au particle.

Oxidizing Role of Cu Cocatalysts in Unassisted Photocatalytic CO2 Reduction Using p-GaN/Al2O3/Au/Cu Heterostructures.

Photocatalytic CO2 reduction to CO under unassisted (unbiased) conditions was recently demonstrated using heterostructure catalysts that combine p-type GaN with plasmonic Au nanoparticles and Cu nanoparticles as cocatalysts (p-GaN/Al2O3/Au/Cu). Here, we investigate the mechanistic role of Cu in p-GaN/Al2O3/Au/Cu under unassisted photocatalytic operating conditions using Cu K-edge X-ray absorption spectroscopy and first-principles calculations. Upon exposure to gas-phase CO2 and H2O vapor reaction conditions, the composition of the Cu nanoparticles is identified as a mixture of CuI and CuII oxide, hydroxide, and carbonate compounds without metallic Cu. These composition changes, indicating oxidative conditions, are rationalized by bulk Pourbaix thermodynamics. Under photocatalytic operating conditions with visible light excitation of the plasmonic Au nanoparticles, further oxidation of CuI to CuII is observed, indicating light-driven hole transfer from Au-to-Cu. This observation is supported by the calculated band alignments of the oxidized Cu compositions with plasmonic Au particles, where light-driven hole transfer from Au-to-Cu is found to be thermodynamically favored. These findings demonstrate that under unassisted (unbiased) gas-phase reaction conditions, Cu is found in carbonate-rich oxidized compositions rather than metallic Cu. These species then act as the active cocatalyst and play an oxidative rather than a reductive role in catalysis when coupled with plasmonic Au particles for light absorption, possibly opening an additional channel for water oxidation in this system.

The Influence of Au Loading and TiO2 Support on the Catalytic Wet Air Oxidation of Glyphosate over TiO2+Au Catalysts

This study aimed to explore the impact of varying amounts of added Au (0.5 to 2 wt.%) and the structural characteristics of anatase TiO2 supports (nanoparticles (TP, SBET = 88 m2/g) and nanorods (TR, SBET = 105 m2/g)) on the catalytic efficiency of TiO2+Au catalysts in eliminating the herbicide glyphosate from aqueous solutions via the catalytic wet air oxidation (CWAO) process. The investigation was conducted using a continuous-flow trickle-bed reactor. Regardless of the TiO2 support and the amount of Au added, the addition of Au has a positive effect on the glyphosate degradation rate. Regarding the amount of Au added, the highest catalytic activity was observed with the TP + 1% Au catalyst, which had a higher Schottky barrier (SB) than the TP + 2% Au catalyst, which helped the charge carriers in the TiO2 conduction band to increase their reduction potential by preventing them from returning to the Au. The role of glyphosate degradation product adsorption on the catalyst surface is crucial for sustaining the long-term catalytic activity of the investigated TiO2+Au materials. This was particularly evident in the case of the TR + 1% Au catalyst, which had the highest glyphosate degradation rate at the beginning of the CWAO experiment, but its catalytic activity then decreased over time due to the adsorption of glyphosate degradation products, which was favoured by the presence of strong acidic sites. In addition, the TR + 1% Au solid had the smallest average Au particle size of all analyzed materials, which were more easily deactivated by the adsorption of glyphosate degradation products. The analysis of the degradation products of glyphosate shows that the oxidation of glyphosate in the liquid phase involves the rupture of C–P and C–N bonds, as amino-methyl-phosphonic acid (AMPA), glyoxylic acid and sarcosine were detected.

Coprecipitation of amorphous silica and gold nanoparticles contributes to gold hyperenrichment

Hyperenrichment of Au in orogenic ores occurs overwhelmingly within quartz veins, but the formation pathway of quartz veins in orogenic systems remains enigmatic. We conducted hydrothermal experiments simulating coprecipitation of Au and amorphous silica and subsequent recrystallization to test whether this is a viable mechanism to generate Au nuggets within quartz veins. Within minutes, coprecipitation of amorphous silica and Au nanoparticles occurred, representing an effective Au deposition mechanism. Within one week, amorphous silica had recrystallized to quartz, causing the coarsening of Au particles and their relocation to quartz grain boundaries and fractures. The experimental textures are similar to those observed in high-grade zones of orogenic gold deposits. In addition to trapping Au, amorphous silica may increase competency contrasts that facilitate short-term fracture reactivation during earthquake aftershock periods or swarms, allowing further Au input from fresh fluids. These findings demonstrate that amorphous silica precipitation may be an important transient stage in orogenic gold deposit formation, with significant implications for metal accumulation in quartz veins.

Development of a flow reactor incorporating polydopamine-poly(ε-caprolactone) with gold particles

Addressing the significant challenge of dye wastewater pollution, this study introduces a novel solution employing a flow catalytic reactor loaded with gold (Au) particles. The reactor utilizes a porous monolithic material with a Poly(ε-caprolactone) (PCL) matrix as the carrier for Au particles, with polydopamine employed to immobilize the Au onto the surface of the PCL monolith. To assess the catalytic efficiency of the reactor, a model catalytic degradation experiment involving the reaction between methyl orange (MO) and sodium borohydride was conducted. The catalytic reaction was facilitated by a peristaltic pump. The reactor setup involved fixing the monolith within a heat shrinkable tube, and the peristaltic pump ensured the flow catalytic reaction. The protective effect of liquid nitrogen was utilized to confirm that the porous structure of the PCL monolith, with its low melting point, remained intact after being fixed in the heat shrink tube. Catalytic results revealed remarkable efficacy, with the decomposition efficiency of MO reaching 98.54%. This flow reactor enables continuous operation, making it more practical for real-world applications compared to traditional batch methods. Furthermore, even after 5 cycles, the sample maintained a catalytic efficiency exceeding 90%, demonstrating the excellent reusability of the reactor.

Lattice-Strained Bimetallic Nanocatalysts: Fundamentals of Synthesis and Structure.

Bimetallic nanostructured catalysts have shown great promise in the areas of energy, environment and magnetics. Tunable composition and electronic configurations due to lattice strain at bimetal interfaces have motivated researchers worldwide to explore them industrial applications. However, to date, the fundamentals of the synthesis of lattice-mismatched bimetallic nanocrystals are still largely uninvestigated for most supported catalyst materials. Therefore, in this work, we have conducted a detailed review of the synthesis and structural characterization of bimetallic nanocatalysts, particularly for renewable energies. In particular, the synthesis of Pt, Au and Pd bimetallic particles in a liquid phase has been critically discussed. The outcome of this review is to provide industrial insights of the rational design of cost-effective nanocatalysts for sustainable conversion technologies.