Noble Metal Precursors Research Articles

A simple Ag-MoS2 hybrid nanozyme-based sensor array for colorimetric identification of biothiols and cancer cells.

The intracellular levels of biothiols are associated with various diseases including cancer, and biothiols are regarded as tumor biomarker. Due to the similarity of the molecular structure of biothiols, the development of simple, rapid, efficient, and sensitive colorimetric sensor arrays holds great promise for clinical cancer diagnosis. Here, we developed a simple Ag-MoS2 hybrid nanozyme-based sensor array for colorimetric identification of biothiols and cancer cells. The novel Ag-MoS2 nanoprobe was synthesized in a simple and efficient way through the in situ self-reduction reaction between MoS2 and noble metal precursor. Benefiting from to the formation of heterogeneous metal structures, the peroxidase (POD)-like catalytic activity of the synthesized Ag-MoS2 hybrid nanocomposites is significantly enhanced compared to MoS2 alone. Moreover, the catalytic activity of Ag-MoS2 nanozyme was correlated with the pH of the reaction solution and the inhibitory effects of the three biothiols on the nanozyme-triggered chromogenic system differed in the specific pH environments. Therefore, each sensing unit of this electronic tongue generated differential colorimetric fingerprints of different biothiols. After principal component analysis (PCA), the developed novel colorimetric sensor array can accurately discriminate biothiols between different types, various concentrations, and different mixture proportions. Further, the sensor array was used for the colorimetric identification of real serum and cellular samples, demonstrating its great potential in tumor diagnostic applications.

Electroless Deposition of Noble Metals on Rod-Shape Plant Viruses in Various Aqueous Metal Precursor Solutions.

The challenge of synthesizing noble metal nanostructures sustainably has encouraged researchers to explore biological routes for nanostructure production, such as biotemplating. Plant viruses with rod-shape morphology, such as tobacco mosaic virus (TMV) and barley stripe mosaic virus (BSMV), offer promising biotemplates to produce metal nanorods. TMV and BSMV can be incubated in aqueous metal precursor solutions to mineralize metals on the coat proteins (CPs) of the viruses. Previous studies have primarily examined palladium (Pd) mineralization on TMV and BSMV using Na2PdCl4 as the Pd precursor. There is limited scientific literature on the effect of using alternative Pd precursor solutions besides Na2PdCl4 such as K2PdCl4 and PdCl2 to mineralize Pd on TMV and BSMV. Past attempts at mineralizing other noble metals such as platinum (Pt) and gold (Au) required an initial layer of Pd to be deposited on the TMV and BSMV biotemplates. In this study, we aimed to expand the understanding of using alternative Pd precursor solutions to mineralize Pd on TMV and BSMV. Additionally, the deposition of Pt and Au onto TMV and BSMV without the need for an initial Pd mineralization layer was achieved using alternative Pt and Au precursors, including K2PtCl4 and AuCl3, respectively. Pd, Pt, and Au were successfully deposited on TMV and BSMV by incubation in aqueous solutions of Na2PdCl4, K2PdCl4, PdCl2, K2PtCl4, and AuCl3. Kinetic studies were also conducted using ultraviolet-visible (UV-vis) spectroscopy to examine the rates at which Pd, Pt, and Au precursor ions were reduced during the mineralization process, mimicking their adsorption onto TMV and BSMV CPs. BSMV adsorbed noble metal precursor ions faster than TMV as determined by UV-vis spectroscopy. While palladium nanorods (PdNRs) offer high electrical conductivity desirable for electronic applications, Pd-coated TMV and BSMV may face limitations due to their organic cores, potentially compromising conductivity. To address this, one approach is to convert the organic core into conductive amorphous carbon through thermal annealing. In this study, in situ transmission electron microscopy was utilized to thermally anneal Pd-TMV2Cys, thereby transforming them into PdNRs with amorphous carbon cores.

A Straightforward Solvent-Pair-Enabled Multicomponent Coassembly Approach toward Noble-Metal-Nanoparticle-Decorated Mesoporous Tungsten Oxide for Trace Ammonia Sensing.

The straightforward synthesis of noble-metal-nanoparticle-decorated ordered mesoporous transition metal oxides remains a great challenge due to the difficulty of balancing the interactions between precursors and templates. Herein, a solvent-pair-enabled multicomponent coassembly (SPEMC) strategy is developed for straightforward synthesis of noble-metal-nanoparticle-decorated nitrogen-doped ordered mesoporous tungsten oxide (abbreviated as NM/N-mWO3, NM=Pt, Rh, Pd). The amphiphilic poly(ethylene oxide)-block-polystyrene (PEO-b-PS) copolymers coassemble with ammonium metatungstate (AMT) clusters and different kinds of hydrophilic noble metal precursors without phase separation. SPEMC synthesis requires no direct interaction between PEO-b-PS and AMT, thus the assembly equilibriums between noble metal precursors and PEO-b-PS can be readily controlled. The obtained NM/N-mWO3 nanocomposites possess ordered mesopores, abundant oxygen vacancies, and metal-metal oxide interfaces. As a result, the Pt/N-mWO3 sensors exhibit superior ammonia sensing performances with high sensitivity, an ultralow limit of detection (51.2 ppb), good selectivity, and long-term stability. Spectroscopic analysis reveals that ammonia is oxidized stepwise to NO, NO2 -, and NO3 - during the sensing process. Moreover, a portable wireless module based on Pt/N-mWO3 sensor can recognize ppm-level concentration of ammonia, which lays a solid foundation for its application in various fields.

Confined Synthesis of Noble Metal Clusters Assisted by Liquid Film for Photocatalytic CO2 Reduction.

The important concept of confined synthesis is considered a promising strategy for the design and synthesis of definable nanostructured materials with controllable compositions and specific morphology, such as highly loaded single-atom catalysts capable of providing abundant active sites for photocatalytic reactions. In recent years, researchers have been working on developing new confined reaction systems and searching for new confined spaces. Here, we present for the first time the concept of a bubble liquid film as a novel confined space. The liquid film has a typical sandwich structure consisting of a water layer, sandwiched between the upper and lower surfactant layers, with the thickness of the intermediate water layer at the micro- and nanometer scales, which can serve as a good confinement. Based on the above understanding and combined with the photodeposition method, we successfully confined synthesized Ag/TiO2, Au/TiO2, and Pd/TiO2 photocatalysts in liquid film. By HAADF-STEM, it can be seen that the noble metal morphologies are all nanoclusters of about 1 nm and are highly uniformly dispersed on the TiO2 surface. Compared with photodeposition in solution, we believe that the surfactant molecular layer restricts a limited amount of precursor to the liquid film, avoiding the accumulation of noble metals and the formation of large particle size nanoparticles. The liquid film, meanwhile, restricts the migration path of noble metal precursors, allowing for thorough in situ photodeposition and enables the complete and uniform dispersion of noble metal precursors, greatly reducing the photodeposition time. The uniform loading of the three noble metals proved the universality of the method, and the catalysts showed high activity for photocatalytic CO2 reduction. The rates of reduction of CO2 to CO over the Ag/TiO2 photocatalytic reached 230 μmol g-1 h-1.This study provides a new idea for the expansion of the confined reaction system and a reference for the study of liquid film as the confined space.

Rapid Synthesis of Noble Metal Colloids by Plasma-Liquid Interactions.

The interactions between plasma and liquids cause complex physical and chemical reactions at the gas-liquid contact surface, producing numerous chemically active particles that can rapidly reduce noble metal ions. This study uses atmospheric-pressure surface dielectric barrier discharge (DBD) plasma to treat ethanol aqueous solutions containing noble metal precursors, and stable gold, platinum, and palladium colloids are obtained within a few minutes. To evaluate the mechanism of the reduction of noble metal precursors by atmospheric-pressure surface DBD plasma, the corresponding metal colloids are prepared first by activating an ethanol aqueous solution with plasma and then adding noble metal precursors. It is found that the long-lived active species hydrogen peroxide (H2O2) plays a dominant role in the synthesis process, which has distinct effects on different metal ions. When HAuCl4 and H2PdCl4 are used as precursors, H2O2 acts as a reducing agent, and AuCl4- and PdCl42- ions can be reduced to metallic Au and Pd. However, when AgNO3 is the precursor, H2O2 acts as an oxidising agent, and Ag+ ions cannot be reduced to obtain metal colloids because metallic Ag can be dissolved in H2O2 under acidic conditions. A similar phenomenon was also observed for the preparation of Pd colloid-PA with a plasma-activated ethanol aqueous solution using Pd(NO3)2 as a Pd precursor.

Synthesis of low-cost multi-element Pt-based alloy nanoparticles as catalysts for the oxygen reduction reaction.

Due to their high catalytic activity, stability, and economic benefits, Pt-based multi-element alloyed nanoparticles (NPs) are considered promising electrodes for oxygen reduction reactions. However, a synthesis method capable of controlling the reduction reaction of elements with different redox potentials to synthesize multimetallic alloy NPs is yet to be developed. In this study, monodisperse NiPtPd alloy NPs with varying compositions were synthesized using 1-heptanol as a reducing solvent. The selection of low-reducing noble metal precursors and complexing agents is done strategically to adjust the reduction time of metal ions. The spectroscopic results confirmed that olelylamine (OAm) preferentially coordinates with Pt ions, while trioctylphosphine (TOP) preferentially coordinates with Pd ions. Consequently, control of the elemental distribution within the particle is successfully achieved by adjusting the OAm/Pt and TOP/Pd molar ratios. Subsequently, Ni78Pt11Pd11 alloy NPs were designed, and their catalytic properties as electrodes in the oxygen reduction reaction (ORR) were examined. Despite a low noble metal content of 22%, the catalytic performance and stability were superior to and comparable to those of commercial Pt NPs, respectively.

Polyhydroxy Fullerene for Synthesizing Noble Metal Nanoparticles

The redox properties of fullerene and its derivatives enable them to function as electron relays through either oxidation or reduction. Polyhydroxy fullerene (PHF), also known as fullerol or fullerenol, is highly water-soluble derivative and a well-known antioxidant. We have found that PHF is also very effective in reducing noble metal precursors and stabilizing metal nanoparticles by forming covalent M-O bonds. Traditionally, noble metal nanoparticles, such as gold are synthesized using a reducing agent like sodium borohydride (NaBH4) or sodium citrate at elevated temperatures and alkaline pH, with stabilizers added during nucleation to control the size and dispersion of the nanoparticles. While sodium citrate is sometimes used as a single reducing and stabilizing agent, it is not an effective stabilizer and is often replaced with polymers to improve colloidal dispersion. In contrast, PHF can be used as a single reducing and stabilizing agent for metal nanoparticles. The nanoparticles were synthesized by simply mixing the metal precursors with PHF in an aqueous phase and stirring at room temperature. The size and morphology of synthesized nanoparticles were characterized with high-resolution transmission electron microscopy, aberration corrected TEM, and dynamic light scattering. These nanoparticles were monodisperse with size ranging from 2 nm to 100 nm in diameter, which could be controlled by changing the concentration of the two reactants. We utilized multiple tools to investigate the mechanism of reduction and nanoparticle formation. We propose a kinetic agglomerate-dissociation mechanism to describe the formation of gold nanoparticles using PHF. Kinetic agglomerates form instantaneously upon mixing the two reactants due to electrostatic interactions. During the reduction process reactive carbonyl peaks were observed with electron energy loss spectroscopy. The carbonyl moieties were observed only after agglomerate formation and subsequently changed to Au-O bonds between PHF and synthesized gold nanoparticles, which was confirmed with Fourier-transform infrared spectroscopy and density-functional theory calculations, and X-ray photoelectron spectroscopy. Further, we demonstrated that the synthesis of gold nanoparticles using PHF can be affected by pH due to changes in hemiketal structure of PHF. Compared to citrate ions, PHF-coated gold nanoparticles are more stable, remaining so for over two years. The novel PHF-mediated synthesis method can also be applied to other noble metals like platinum, palladium, and silver and create bimetallic nanoparticles. The surface PHF coating on noble metal nanoparticles integrates the properties of both metal and carbon nanoparticles, resulting in superior functional applications. Our findings open up new opportunities for metallic nanoparticle preparation methods, properties, and applications.

Efficient predictions of cytotoxicity of TiO2-based multi-component nanoparticles using a machine learning-based q-RASAR approach

The availability of experimental nanotoxicity data is in general limited which warrants both the use of in silico methods for data gap filling and exploring novel methods for effective modeling. Read-Across Structure-Activity Relationship (RASAR) is an emerging cheminformatic approach that combines the usefulness of a QSAR model and similarity-based Read-Across predictions. In this work, we have generated simple, interpretable, and transferable quantitative-RASAR (q-RASAR) models which can efficiently predict the cytotoxicity of TiO2-based multi-component nanoparticles. A data set of 29 TiO2-based nanoparticles with specific amounts of noble metal precursors was rationally divided into training and test sets, and the Read-Across-based predictions for the test set were generated. The optimized hyperparameters and the similarity approach, which yield the best predictions, were used to calculate the similarity and error-based RASAR descriptors. A data fusion of the RASAR descriptors with the chemical descriptors was done followed by the best subset feature selection. The final set of selected descriptors was used to develop the q-RASAR models, which were validated using the stringent OECD criteria. Finally, a random forest model was also developed with the selected descriptors, which could efficiently predict the cytotoxicity of TiO2-based multi-component nanoparticles superseding previously reported models in the prediction quality thus showing the merits of the q-RASAR approach. To further evaluate the usefulness of the approach, we have applied the q-RASAR approach also to a second cytotoxicity data set of 34 heterogeneous TiO2-based nanoparticles which further confirmed the enhancement of external prediction quality of QSAR models after incorporation of RASAR descriptors.

Fabrication of PtIrPd Noble Metal Medium Entropy Alloy Thin Film by Atomic Layer Deposition

Noble metal medium entropy alloy (MEA) thin films have recently attracted enormous research interests recently because of their great potential in the catalytic application. However, conventional bottom‐up fabrication methods for MEA thin film such as magnetron sputtering face enormous challenges including precise control over film thickness and consumption of costly high‐purity noble metal targets. Herein, a facile and tunable approach is developed coupling sequential atomic layer deposition (ALD) of noble metal layers with electric Joule heating (EJH) alloying process to grow platinum‐iridium‐palladium (PtIrPd) MEA thin films. The PtIrPd MEA thin film with a thickness of ≈20 nm and an atomic ratio of 35:35:30 is successfully fabricated. The effect of EJH processing temperature on the film morphology and structure evolution is investigated. ALD provides flexibility in the metal deposition sequence with meticulous thickness control and atomic composition precision, while the ultrafast EJH ramping/cooling rates promote homogeneous alloying of MEA combinations inhibiting phase separation. Furthermore, the integrated method circumvents a major obstacle of finding a common ALD temperature window for different noble metal precursors as well as opens new pathways for the controllable synthesis of multicomponent metal alloy thin films with potential catalytic, magnetic, and optical properties.

High-Entropy-Alloy Nanocrystal Based Macro- and Mesoporous Materials.

High-entropy-alloy (HEA) nanoparticles are attractive for several applications in catalysis and energy. Great efforts are currently devoted to establish composition-property relationships to improve catalytic activity or selectivity. Equally importantly, developing practical fabrication methods for shaping HEA-based materials into complex architectures is a key requirement for their utilization in catalysis. However, shaping nano-HEAs into hierarchical structures avoiding demixing or collapse remains a great challenge. Herein, we overcome this issue by introducing a simple soft-chemistry route to fabricate ordered macro- and mesoporous materials based on HEA nanoparticles, with high surface area, thermal stability, and catalytic activity toward CO oxidation. The process is based on spray-drying from an aqueous solution containing five different noble metal precursors and polymer latex beads. Upon annealing, the polymer plays a double role: templating and reducing agent enabling formation of HEA nanoparticle-based porous networks at only 350 °C. The formation mechanism and the stability of the macro- and mesoporous materials were investigated by a set of in situ characterization techniques; notably, in situ transmission electron microscopy unveiled that the porous structure is stable up to 800 °C. Importantly, this process is green, scalable, and versatile and could be potentially extended to other classes of HEA materials.

The roles of gold and silver nanoparticles on ZnIn2S4/silver (gold)/tetra(4-carboxyphenyl)porphyrin iron(III) chloride hybrids in carbon dioxide photoreduction

The construction of hybrid catalysts composed of inorganic semiconductors and molecular catalysts shows great potential for achieving high photocatalytic carbon dioxide (CO2) conversion efficiency. In this study, ZnIn2S4 was first synthesized via a solvothermal route. Gold (Au) and silver (Ag) nanoparticles were then deposited on ZnIn2S4 via the reduction of noble metal precursor by sulfur vacancy defects. The obtained composite was further combined with tetra(4-carboxyphenyl)porphyrin iron(III) chloride (FeTCPP) molecular catalyst for efficient photocatalytic CO2 conversion. The roles of different noble metal nanoparticles in charge separation and interfacial electron transfer have been comprehensively studied. The photocatalytic performance and photoelectrochemical characterizations demonstrate that the introduction of Ag or Au nanoparticles is beneficial for charge separation. More importantly, the presence of Ag nanoparticles plays a crucial role in promoting the interfacial charge transfer between ZnIn2S4 and FeTCPP, whereas, Au nanoparticles function as active sites for the water reduction reaction.

Facile Synthesis of Porous Ag Crystals as SERS Sensor for Detection of Five Methamphetamine Analogs.

Porous noble metal nanomaterials have attracted extensive attention due to their high specific surface area and surface plasmon resonance effect. However, it is difficult to form porous structures due to the high mobility and low reduction potential of noble metal precursors. In this article, we developed a facile method for preparing porous Ag with a controllable structure at room temperature. Two kinds of Ag crystals with different porous structures were successfully prepared by using AgCl cubes as sacrificial templates. Through the galvanic replacement reaction of Zn and AgCl, Ag crystals with a sponge-like porous structure were successfully prepared. Additionally, using NaBH4 as the reducing agent, we prepared granular porous Ag cubes by optimizing the amount of reducing agent. Both the sponge-like and granular porous Ag cubes have clean and accessible surfaces. In addition, we used the prepared two porous Ag cubes as substrate materials for SERS detection of five kinds of methamphetamine analogs. The experimental results show that the enhancement effect of granular porous Ag is better than that of sponge-like porous Ag. Furthermore, we probed the hot spot distribution of granular porous Ag by Raman mapping. By using granular porous Ag as the substrate material, we have achieved trace detection of 5 kinds of methamphetamine analogs including Ephedrine, Amphetamine, N-Methyl-1-(benzofuran-5-yl)propan-2-amine (5-MAPB), N-Methyl-1-(4-methoxyphenyl)propan-2-amine (PMMA) and N-Methyl-1-(4-fluorophenyl)propan-2-amine (4-FMA). Furthermore, to achieve qualitative differentiation of analogs with similar structures we performed density functional theoretical (DFT) calculations on the Raman spectra of the above analogs. The DFT calculations provided the vibrational frequencies, Raman activities, and normal mode assignment for each analog, enabling the qualitative differentiation of the above analogs.

Catalytic performance and SO2 resistance of zirconia-supported platinum-palladium bimetallic nanoparticles for methane combustion

Methane can induce a serious greenhouse effect, and it is highly required to control its emissions. In this work, we used PdCl2 and H2PtCl6 as noble metal precursors, polyvinyl alcohol as protecting agent, and NaBH4 as reducing agent to synthesize the PtPdx bimetallic nanoparticles (NPs), which were then supported on the surface of zirconia to generate the yPtPdx/ZrO2 (i.e., 0.44PtPd2.20/ZrO2, 0.54PtPd0.90/ZrO2, and 0.61PtPd0.48/ZrO2; x and y are the Pd/Pt molar ratio and PtPdx loading, respectively; x = 0.48–2.20; and y = 0.44–0.61 wt%) catalysts. For comparison purposes, we also prepared the 0.55 wt% Pd/ZrO2 (0.55 Pd/ZrO2) and 0.65 wt% Pt/ZrO2 (0.65Pt/ZrO2) catalysts. It was shown that the PtPdx NPs with an average size of 2.4–3.6 nm were highly dispersed on the ZrO2 support. Among these samples, 0.44PtPd2.20/ZrO2 exhibited the best catalytic activity (T50% = 345 °C and T90% = 408 °C at space velocity = 20,000 mL/(g h); apparent activation energy = 59 kJ/mol; turnover frequency (TOFPd) at 350 °C = 124.1 × 10–3 s−1, and specific reaction rate at 350 °C = 466.6 μmol/(gPd s)). The good performance of 0.44PtPd2.20/ZrO2 was associated with its well dispersed PtPd2.20 NPs, high adsorbed oxygen species concentration, good redox ability, large methane adsorption capacity, and strong interaction between PtPdx and ZrO2. Furthermore, the 0.44PtPd2.20/ZrO2 catalyst also possessed excellent thermal stability and good water- and sulfur dioxide-resistant performance. According to the characterization results, we deduce that SO2 could be preferentially adsorbed at the Pt site in 0.44PtPd2.20/ZrO2 and protected the active phase of PdO from being poisoned by SO2, thus improving its SO2 resistance.

Interfacial Reduction Nucleation of Noble Metal Nanodots on Redox-Active Metal-Organic Frameworks for High-Efficiency Electrocatalytic Conversion of Nitrate to Ammonia.

Electrochemically converting nitrate to ammonia is a promising route to realize artificial nitrogen recycling. However, developing highly efficient electrocatalysts is an ongoing challenge. Herein, we report the construction of stable and redox-active zirconium metal-organic frameworks (Zr-MOFs) based on Zr6 nanoclusters and redox-reversible tetrathiafulvalene (TTF) derivatives as inorganic nodes and organic linkers, respectively. The redox-active Zr-MOF can facilitate the in situ reduction of noble metal precursors free of external reductants and realize the uniform nucleation of noble metal nanodots (NDs) on Zr-MOF, achieving the preparation of M-NDs/Zr-MOF (M = Pd, Ag, or Au). The highly porous Zr-MOF with good conductivity can facilitate the mass transfer process. Among the M-NDs/Zr-MOF catalysts, Pd-NDs/Zr-MOF exhibits the highest electrocatalytic activity, delivering a NH3 yield of 287.31 mmol·h-1·g-1cat. and a Faradaic efficiency of 58.1%. The proposed interfacial reduction nucleation strategy for anchoring M NDs on Zr-MOFs can be applied to other challenging energy conversion reactions.

Rationally Designed Dual‐Mesoporous Transition Metal Oxides/Noble Metal Nanocomposites for Fabrication of Gas Sensors in Real‐Time Detection of 3‐Hydroxy‐2‐Butanone Biomarker

AbstractTransition metal oxides/noble metal (TMOs/NM) nanocomposites are one kind of important material for semiconductor gas sensors. The controllable construction of a highly connected mesoporous structure and easily accessible active sites is essential for gas sensing performance but remains a great challenge. Herein, a soluble mercapto phenolic resin polymer mediated co‐assembly approach is proposed for the construction of ordered dual mesoporous structure and the simultaneous loading of highly dispersed noble metal nanoparticles. The home‐made soluble mercapto phenolic resin polymer enabled the co‐assembly of transition metal precursors, noble metal precursors, and poly(ethylene oxide)‐block‐polystyrene (PEO‐b‐PS) micelles, resulting in a straightforward synthesis of ordered dual‐mesoporous TMOs/NM nanocomposites (e.g., WO3/Au, TiO2/Au, NbOx/AuPd). As proof of the concept, the synthesized dual‐mesoporous WO3/Au materials are applied for sensing of 3‐hydroxy‐2‐butanone, a biomarker of food‐borne pathogenic bacteria Listeria monocytogenes. The sensors exhibit high sensitivity (Ra/Rg = 18.8 to 2.5 ppm) and high selectivity based on their noble metal sensitization and superior mesopore connectivity for gas diffusion. Furthermore, the synthesized gas sensors are integrated into a wireless sensing module connected to a smartphone, providing a rapid and convenient real‐time detection of 3‐hydroxy‐2‐butanone.

Noble metal aerogels rapidly synthesized by ultrasound for electrocatalytic reaction

Noble metal aerogels (NMAs), belonging to the porous material, have exhibited excellent catalytic performance. Although the synthesis method continues to improve, it still exists some problems which hindered the experimental process, such as high concentration of noble metal precursors, long synthesis cycle, expensive production cost, and uncontrollable ligament length. In this work, ultrasonic wave and reducing agent NaBH4 were simultaneously applied to gelation process. With the cavitation of ultrasound, it can generate huge energy with heating and stirring, thus gelation reaction proceeded quickly, and even completed the process in only a few seconds, that is much faster than the recorded. A wide concentration range was successfully expanded from 0.02 mmol/L to 62.5 mmol/L. Further, we extended this method to a variety of noble metal elements (Au, Ru, Rh, Ag, Pt, Pd), and this method is adaptive for the synthesis of single metal aerogels (Au, Ag, Ru, Rh, Pd), bimetal and trimetal aerogels (Au-Ag, Au-Rh, Au-Ru, Au-Pt, Au-Pd, Au-Pt-Pd). In addition, the ligament size of alloy aerogels are 10 nm or less. Moreover, their brilliant properties were demonstrated in hydrogen evolution reaction (HER) and ethanol oxidation reaction (EOR).

Structurally and Compositionally Tunable Absorption Properties of AgCl@AgAu Nanocatalysts for Plasmonic Photocatalytic Degradation of Environmental Pollutants

Composite nanomaterials having Ag nanoparticles (NPs) that decorate nanostructured AgCl (Ag/AgCl) are promising as plasmonic photocatalysts because of the visible-light absorption of Ag NPs. However, the narrow absorption bands of Ag NPs near 400 nm cause inefficient absorption in the visible range and, consequently, unsatisfactory photocatalytic activity of Ag/AgCl nanomaterials. In this study, we introduce a new class of AgCl-based photocatalysts that are decorated with bimetallic Ag and Au NPs (AgCl@AgAu NPs) for visible-light-driven photocatalytic degradation of organic pollutants. Polyvinylpyrrolidone induces selective reduction of noble metal precursors on AgCl while leaving AgCl intact. The extended composition of the decorating NPs red-shifts the absorption band to 550–650 nm, which allows the catalysts to take advantage of more energy in the visible range for improved efficiency. Furthermore, we control the structures of the AgCl@AgAu NPs, and investigate their correlation with photocatalytic properties. The versatility, chemical stability, and practical application of the AgCl@AgAu NPs are demonstrated using various organic pollutants, recycling experiments, and natural aqueous media, respectively. Our fundamental investigation on the synthesis and applications of AgCl-based nano-photocatalysts is highly valuable for designing plasmonic photocatalysts and expanding their utilization.

Engineering the epitaxial interface of Pt-CeO2 by surface redox reaction guided nucleation for low temperature CO oxidation

The interface between metal nanoparticles (NPs) and support plays a vital role in catalysis because both electron and atom exchanges occur across the metal-support interface. However, the rational design of interfacial structure facilitating the charge transfer between the neighboring parts remains a challenge. Herein, a guided nucleation strategy based on redox reaction between noble metal precursor and support-surface is introduced to construct epitaxial interfaces between Pt NPs and CeO2 support. The Pt/CeO2 catalyst exhibits near room temperature catalytic activity for CO oxidation that is benefited from the well-defined interface structure facilitating charge transfer from CeO2 support to Pt NPs. Meanwhile, this general approach based on support-surface-induced-nucleation was successfully extended to synthesize Pd and Cu nanocatalysts on CeO2, demonstrating its universal and feasible characteristics. This work is an important step towards developing highly active supported metal catalysts by engineering their interfaces.

Noble Metal Particles Confined in Zeolites: Synthesis, Characterization, and Applications.

Noble metal nanoparticles or subnanometric particles confined in zeolites, that is, metal@zeolite, represent an important type of functional materials with typical core–shell structure. This type of material is known for decades and recently became a research hotspot due to their emerging applications in various fields. Remarkable achievements are made dealing with the synthesis, characterization, and applications of noble metal particles confined in zeolites. Here, the most representative research progress in metal@zeolites is briefly reviewed, aiming to boost further research on this topic. For the synthesis of metal@zeolites, various strategies, such as direct synthesis from inorganic or ligand‐assisted noble metal precursors, multistep postsynthesis encapsulation and ion‐exchange followed by reduction, are introduced and compared. For the characterization of metal@zeolites, several most useful techniques, such as electron microscopy, X‐ray based spectroscopy, infrared and fluorescence emission spectroscopy, are recommended to check the successful confinement of noble metal particles in zeolite matrix and their unique physiochemical properties. For the applications of metal@zeolites, catalysis and optics are involved with an emphasis on catalytic applications including the size‐dependent catalytic properties, the sintering‐resistance properties, the substrate shape‐selective catalysis, and catalysis modulation by zeolite microenvironment.

Surfactant-free room temperature synthesis of PdxPty/C assisted by ultra-sonication as highly active and stable catalysts for formic acid oxidation

Abstract Formic acid oxidation is usually catalyzed on PdPt bimetallic catalysts, which are synthesized by co-reduction of noble metal precursors in the presence of high molecular capping agents. In this work, surfactant-free PdxPty/C catalysts are synthesized by H2 reduction in ethylene glycol assisted with ultrasonication vibration at room temperature. Nanoparticle agglomeration in the course of preparation has been sufficiently curbed by strong mechanical ultrasonication instead of traditionally-employed surfactants. As a result, “clean” surfactant-free PdxPty/C catalysts necessitate only simple washing before collection. The catalysts are characterized by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The compositionally optimized Pd100Pt1/C catalyst registers a mass activity of 3171 A g−1 (Pt + Pd) for formic acid oxidation in 0.5 M H2SO4+0.5 M HCOOH, which lists one of the best results reported so far and surpasses that of a commercial Pd/C by 5.6 times. Stability of the catalysts is investigated by cyclic voltammetric as well as chronoamperometric evaluations. This work offers a convenient and environmentally benign room-temperature route to synthesize highly active and stable catalysts for formic acid oxidation.