Alloy Nanoclusters Research Articles

Ag10Cu16 nanoclusters with triple-ligand protection: total structure and electronic structure analysis.

Illustrating the molecular structure of metal nanoclusters with the protection of multiple ligands is a prerequisite to understand structure-property relationships of nano or bulk materials with hybrid interfaces. Reported herein is the synthesis, total structure and electronic structure analysis of a new Ag/Cu alloy nanocluster with triple-ligand protection. The cluster with the formula of Ag10Cu16(C8H9S)16(PPh3)4(CF3CO2)8 has been attained in one-pot in a simple way. X-ray single crystal analysis displays its unique metal framework and more importantly rich interface structures. The ligands of phosphine, thioate and carboxylic acid are coordinated to the surface of the cluster in distinctive modes. The electronic structure of the cluster has been revealed by density functional theory, showing that it is a 2-electron superatom with jellium configurations of 1S2. In good accordance with the closure of the geometric and electronic structures, the cluster exhibits moderate stability, which makes it a candidate for further application in many fields.

From M6 to M12, M19 and M38 molecular alloy Pt-Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters.

Heterometallic Chini-type clusters [Pt6-xNix(CO)12]2- (x = 0-6) were obtained by reactions of [Pt6(CO)12]2- with Ni-clusters such as [Ni6(CO)12]2-, [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, or from [Pt9(CO)18]2- and [Ni6(CO)12]2-. The Pt/Ni composition of [Pt6-xNix(CO)12]2- (x = 0-6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt9(CO)18]2- with [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, as well as reactions of [Pt12(CO)24]2- with [Ni6(CO)12]2-, [Ni9(CO)18]2- and [H2Ni12(CO)21]2-, afforded [Pt9-xNix(CO)18]2- (x = 0-9) species. [Pt6-xNix(CO)12]2- (x = 1-5) were converted into [Pt12-xNix(CO)21]4- (x = 2-10) upon heating in CH3CN at 80 °C, with almost complete retention of the Pt/Ni composition. Reaction of [Pt12-xNix(CO)21]4- (x ≈ 8) with HBF4·Et2O afforded the [HPt14+xNi24-x(CO)44]5- (x ≈ 0.7) nanocluster. Finally, [Pt19-xNix(CO)22]4- (x = 2-6) could be obtained by heating [Pt9-xNix(CO)18]2- (x = 1-3) in CH3CN at 80 °C, or [Pt6-xNix(CO)12]2- (2-4) in DMSO at 130 °C. The molecular structures of these new alloy nanoclusters have been determined by single crystal X-ray diffraction. The site preference of Pt and Ni within their metal cages has been computationally investigated. The electrochemical and IR spectroelectrochemical behavior of [Pt19-xNix(CO)22]4- (x = 3.11) has been studied and compared to the isostructural homometallic nanocluster [Pt19(CO)22]4-.

An alkynyl-protected Ag13-xCu6+x nanocluster for catalytic hydrogenation.

A novel alkynyl-stabilized silver-copper alloy nanocluster with the composition of [Ag13-xCu6+x(tBuC6H4CC)14(PPh3)6](SbF6)3 was prepared by the (PPh3)2CuBH4-mediated reduction approach. The nanocluster features a centred disordered-octahedral Ag7Cu6 kernel, which is protected by hybrid alkynyl and triphenylphosphine ligands. Structural comparison of this two-electron nanocluster with other alkynyl-capped Ag/Cu ones suggested that the structure of alkynyl ligands played an important role in dictating the structures of the resulting nanoclusters. The title cluster showed high performance in the catalytic hydrogenation of 4-nitrophenol, indicative of the bright future of cluster-based catalysts.

A bimetallic Ag15Cu12(S-c-C6H11)18(CH3COO)3 nanocluster featuring an irregular Ag12 kernel.

Here, we report the synthesis and atomic structure of a Ag15Cu12(SR)18(CH3COO)3·(C6H14) nanocluster (Ag15Cu12 for short, SR denotes cyclohexanethiol), confirmed by single-crystal X-ray diffraction (SC-XRD), electrospray ionization mass spectrometry (ESI-MS), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). X-ray crystallographic analysis revealed that Ag15Cu12 consisted of an irregular Ag12 core, stabilized by the Ag3Cu12(SR)18(CH3COO)3 shell. The shell consisted of two nearly planar Cu3(SR)6 moieties, three monomeric [-SR-Ag-SR-] units and three Cu2(CH3COO) staples. Furthermore, time-dependent density functional theory (TD-DFT) simulation was performed to interpret the optical absorption features of Ag15Cu12. Overall, this work will broaden and deepen the understanding of Ag-Cu alloy nanoclusters.

Alloying and dealloying of Au18Cu32 nanoclusters at precise locations via controlling the electronegativity of substituent groups on thiol ligands.

The doping site of metals in an alloy nanocluster plays a key role in determining the cluster properties. Herein, we found that alloying engineering was achieved by replacing Cu at specific positions in the second layer Cu20 shell of the [Au18Cu32(SR-O)36]2- or [Au18Cu32(SR-F)36]3- (SR-O = -S-PhOMe; SR-F = -SC6H33,4F2) nanocluster with Au to generate a core-shell [Au20.31Cu29.69(SR-O)36]2- protected by mercaptan ligands with electron-donating substituents, which could be stable obtained compared with the alloyed nanocluster with electron-withdrawing substituent ligands. Moreover, dealloying engineering was accomplished by an electron-withdrawing substituent ligand exchange strategy (i.e., [Au18Cu32(SR-F)36]2-). The abovementioned reaction was analyzed using single-crystal X-ray crystallography, electrospray ionization mass spectrometry, and X-ray photoelectron spectroscopy and monitored via time-dependent ultraviolet-visible absorption spectroscopy. This reversible and precise location of alloying and dealloying provides the possibility for studying the relationship between the structure and properties of nanoclusters at the atomic level.

Structure, optical properties, and catalytic applications of alkynyl-protected M4Rh2 (M = Ag/Au) nanoclusters with atomic precision: a comparative study.

We report two atomically precise alloy nanoclusters of Ag4Rh2(CCArF)8(PPh3)2 and Au4Rh2(CCArF)8(PPh3)2 (Ar = 3,5-(CF3)2C6H3, abbreviated as Ag4Rh2 and Au4Rh2, respectively) co-protected by alkynyl and phosphine ligands. Both clusters have identical octahedral metal core configurations and can be termed superatoms with two free electrons. However, they possess different optical features, manifested by totally different absorbance peaks, and drastically different emission peaks, and also, Ag4Rh2 has a much higher fluorescence quantum yield (18.43%) than Au4Rh2 (4.98%). Moreover, Au4Rh2 exhibited markedly superior catalytic performance in the electrochemical hydrogen evolution reaction (HER), manifested by a much lower overpotential at 10 mA cm-2 and better stability. Density functional theory (DFT) calculations revealed that the free energy change of Au4Rh2 for the adsorption of two H* (0.64 eV) is lower than that of Ag4Rh2 for the adsorption of one H* (-0.90 eV) after stripping a single alkynyl ligand from the cluster. In contrast, Ag4Rh2 demonstrated much stronger catalytic capability for catalyzing 4-nitrophenol reduction. The present study provides an exquisite example to understand the structure-property relationship of atomically precise alloy nanoclusters, and emphasizes the importance of fine-tuning of the physicochemical properties and catalytic performance of the metal nanoclusters through modulating the metal core and beyond.

Solid-phase synthesis of ultra-small CuMo solid solution alloy for efficient electroreduction CO2-to-C2+ production.

We report a fascinating solid-phase synthesis of ultra-small CuMo solid solution alloy nanoclusters (2.1 nm) anchored on electrospun carbon nanofibers (CuMo/CNFs). By tuning the weight ratio of Cu and Mo, the optimized Cu2Mo1/CNFs achieves excellent CO2RR performance with a high faradaic efficiency (FE) of 84.5% for C2+ products and an FEethanol of 75.7%. In situ characterization demonstrates that the Cu2Mo1 alloy can strengthen the adsorption of the crucial intermediate and promote C-C coupling, leading to high selectivity and efficiency for C2+ products.

Preparation of Sub-1 nm Pt3Co Nanoclusters via a Seed-Densification Strategy for Enhanced O2 Capture in Low-Pt-Loading Fuel Cells

Improving O2 capture efficiency by forming densely distributed sub-1 nm Pt alloy nanoclusters is an effective route to enhance the performance of low-Pt-loading membrane electrode assemblies (MEAs). Herein we report a seed-densification strategy in which, when the same amount of Pt precursor is applied, the denser Co seeds lead to smaller Pt3Co alloy nanocrystals due to there being fewer Pt atoms captured by a single seed. In H2–O2 MEA tests, the mass-transfer-limiting current density of the Pt3Co-0.87 cathode is 6.5% and 29.1% higher than those of Pt3Co-1.49 and Pt3Co-3.47, respectively, and in H2–air supply, the corresponding improving rates reach as high as 20.5% and 74.5%. This improvement is well ascribed to the greatly boosted O2 capture efficiency brought by the ultra-tiny Pt3Co nanoclusters with especially dense dispersion in the catalytic layer.

Body-Centered-Cubic-Kernelled Ag15Cu6 Nanocluster with Alkynyl Protection: Synthesis, Total Structure, and CO2 Electroreduction.

While atomically monodisperse nanostructured materials are highly desirable to unravel the size- and structure-catalysis relationships, their controlled synthesis and the atomic-level structure determination pose challenges. Particularly, copper-containing atomically precise alloy nanoclusters are potential catalyst candidates for the electrochemical CO2 reduction reaction (eCO2RR) due to high abundance and tunable catalytic activity of copper. Herein, we report the synthesis and total structure of an alkynyl-protected 21-atom AgCu alloy nanocluster [Ag15Cu6(C≡CR)18(DPPE)2]-, denoted as Ag15Cu6 (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene; DPPE: 1,2-bis(diphenylphosphino)ethane). The single-crystal X-ray diffraction reveals that Ag15Cu6 consists of an Ag11Cu4 metal core exhibiting a body-centered cubic (bcc) structure, which is capped by 2 Cu atoms, 2 Ag2DPPE motifs, and 18 alkynyl ligands. Interestingly, the Ag15Cu6 cluster exhibits excellent catalytic activity for eCO2RR with a CO faradaic efficiency (FECO) of 91.3% at -0.81 V (vs the reversible hydrogen electrode, RHE), which is much higher than that (FECO: 48.5% at -0.89 V vs RHE) of Ag9Cu6 with bcc structure. Furthermore, Ag15Cu6 shows superior stability with no significant decay in the current density and FECO during a long-term operation of 145 h. Density functional theory calculations reveal that the de-ligated Ag15Cu6 cluster can expose more space at the pair of AgCu dual metals as the efficient active sites for CO formation.

The one-step direct synthesis and structure of Au12Ag27Cu5 nanocluster

Ternary Au 12 Ag 27 Cu 5 alloy nanoclusters were rapidly synthesized of by one-step method. The molecular structure has exceptionally high symmetry, and it contains of a two-shell Au 12 @Ag 20 Keplerate core protected by five AgCu(SR) 5 units and one Ag 2 (SR) 5 unit. • Noble metal nanoclusters protected by various ligands have precise atomic arrangement and quantum size effects, which have been widely used in different research fields, such as electrochemistry, sensors, biology and catalysis. • With respect to alloy nanoclusters, the intermetal synergistic effect alters the electronic structure and physicochemical properties, resulting in enhanced performance in luminescence, catalysis, and stability, in comparison with single metal nanoclusters. • The single and binary alloy nanoclusters were widely synthesized. • There are only a few reports on the synthesis and structure of ternary nanoclusters. • Therefore, the synthesis of ternary alloy nanoclusters is lack. • Herein, we employed the one-step rapid synthesis to obtain Au 12 Ag 27 Cu 5 ternary nanocluster. • And the crystal structure was determined by X-ray crystallography. • Our research provides a simple one-step method to construct ternary alloy metal nanoclusters Metal nanoclusters have precise atomically structures, quantum size effect and molecule-like properties, intriguing great potential for applications in various fields. Controlling synthesis of nanocluster is very important in nanoscience. Here, we presented a new strategy for one-step simple synthesis of ternary alloy Au 12 Ag 27 Cu 5 nanoclusters. The atomically precise crystal structure was determined by X-ray crystallography. The optical property of Au 12 Ag 27 Cu 5 nanocluster shows the absorption peaks at 363, 478, 528 and 619 nm. This research provides a one-pot method to construct ternary alloy metal nanoclusters.

Pd3Co1 Alloy Nanocluster on the MWCNT Catalyst for Efficient Formic Acid Electro-Oxidation

In this study, the Pd3Co1 alloy nanocluster from a multiwalled carbon nanotube (MWCTN) catalyst was fabricated in deep eutectic solvents (DESs) (referred to Pd3Co1/CNTs). The catalyst shows a better mass activity towards the formic acid oxidation reaction (FAOR) (2410.1 mA mgPd-1), a better anti-CO toxicity (0.36 V) than Pd/CNTs and commercial Pd/C. The improved performance of Pd3Co1/CNTs is attributed to appropriate Co doping, which changed the electronic state around the Pd atom, lowered the d-band of Pd, formed a new Pd-Co bond act at the active sites, affected the adsorption of the toxic intermediates and weakened the dissolution of Pd; moreover, with the assistance of DES, the obtained ultrafine Pd3Co1 nanoalloy exposes more active sites to enhance the dehydrogenation process of the FAOR. The study shows a new way to construct a high-performance Pd-alloy catalyst for the direct formic acid fuel cell.

Ultrasmall bimetallic Ru-Co alloy nanoclusters immobilized in amino-functionalized UiO-66 and N-doped carbonaceous zirconium oxide nanocomposite for hydrogen generation

To satisfy global energy demands and maintain sustainable levels of atmospheric greenhouse gases, alternative energy sources are required. H 2 generation from hydrolysis of NaBH 4 represents as a safe and convenient method for storing and releasing H 2 . The free amine groups (NH 2 ) and the big pores in the NH 2 -UiO-66 metal-organic framework were exploited to encapsulate ultrasmall bimetallic Ru-Co alloy nanoclusters and monometallic Ru and Co nanoclusters with an average particle size of 1.5 nm via direct anionic exchange technique. To prove the role of the NH 2 groups and the MOF’s pores in the creation of a well and uniform-dispersed ruthenium and cobalt nanoclusters, the NH 2 -UiO-66 was calcined at 600 °C for 3 h in the air to prepare N-doped carbonaceous ZrO 2 (ZrO 2 N @ C) nanocomposite. Hydrazine hydrate (HH) was used as a reducing agent in the presence of microwave irradiation (MWI). The prepared catalysts were used as novel catalysts for hydrogen generation, via the hydrolysis of sodium borohydride (NaBH 4 ). 2 wt% Ru-Co/NH 2 -UiO-66 displays a high hydrogen generation rate (HGR) of 10526 mL H 2 g −1 min −1 from low concentration NaBH 4 solution (50 mM). The extraordinary catalytic activity of the prepared catalysts attributes to the ultrasmall particle size of the ruthenium and cobalt nanoclusters in the MOF’s pores, the synergistic harmony between the Ru and Co nanoclusters in the alloy form, and the large surface area of the NH 2 -UiO-66. The effect of the NaBH 4 concentration, catalyst amount, and reaction temperatures (30–60 °C) was investigated. The catalyst shows high recyclability efficiency for at least five cycles, due to the high leaching resistance of the alloy nanoclusters within the MOF host. The prepared catalysts may be considered as highly efficient catalysts for energy-based applications. • Preparation of ultrasmall single alloy Ru-Co nanoclusters without ligand. • The free amine groups in the NH 2 -UiO-66 provide coordination sites for metal ions. • Synthesis of N-doped carbonaceous ZrO 2 (ZrO 2 N @ C) derived from NH 2 -UiO-66. • Reduction of Ru and Co ions with hydrazine hydrate under MWI. • Ru-Co/NH 2 -UiO-66 achieves a high hydrogen generation rate of 10526 mL g cat −1 min −1 .

Hydrogen generation of single alloy Pd/Pt quantum dots over Co3O4 nanoparticles via the hydrolysis of sodium borohydride at room temperature

To satisfy global energy demands and decrease the level of atmospheric greenhouse gases, alternative clean energy sources are required. Hydrogen is one of the most promising clean energy sources due to its high chemical energy density and near-zero greenhouse gas emissions. A single alloyed phase of Pd/Pt nanoclusters as quantum dots (QDs) was prepared and loaded over Co3O4 nanoparticles with a low loading percentage (1 wt.%) for hydrogen generation from the hydrolysis of NaBH4 at room temperature. L-glutathione (SG) was used as a capping ligand. It was found that the single alloy catalyst (Pd0.5–Pt0.5)n(SG)m/Co3O4 caused a significant enhancement in hydrogen generation in comparison to the monometallic clusters (Pdn(SG)m and Ptn(SG)m). Moreover, the Pd/Pt alloy showed a positive synergistic effect compared to the physical mixture of Pd and Pt clusters (1:1) over Co3O4. The QDs alloy and monometallic Pd and Pt clusters exhibited well-dispersed particle size in ~ 1 nm. The (Pd0.5–Pt0.5)n(SG)m)/Co3O4 catalyst offers a high hydrogen generation rate (HGR) of 8333 mL min− 1 g− 1 at room temperature. The synergistic effect of Pd and Pt atoms in the nanoclusters alloy is the key point beyond this high activity, plus the prepared clusters' unique atomic packing structure and electronic properties. The effect of the NaBH4 concentration, catalyst amount, and reaction temperature (25–60 °C) were investigated, where HGR reaches 50 L min− 1 g− 1 at 60 °C under the same reaction conditions. The prepared catalysts were analyzed by UV–Vis, TGA, HR-TEM, XRD, and N2 adsorption/desorption techniques. The charge state of the Pd and Pt in monometallic and alloy nanoclusters is zero, as confirmed by X-ray photoelectron spectroscopy analysis. The catalysts showed high recyclability efficiency for at least five cycles due to the high leaching resistance of the alloy nanoclusters within the Co3O4 host. The prepared catalysts are highly efficient for energy-based applications.

Unusual Role of the Surfactant in the Self-Assembly of Pt Alloy in Ordered Mesoporous Carbon: Tuning the Nanocluster Size

In the one-step self-assembly synthesis of metallic nanocrystals in ordered mesoporous carbon (OMC), the surfactant functionalizes well as the structure directing agent and mesopore template. Interestingly, this work demonstrates another unusual role the surfactant plays: tuning the size of the nanocrystals. Our investigation shows that the decreasing molecular weight of the PS segment of PEO-b-PS leads to sequentially reduced PtRu particle sizes of 4.4, 3.9, and 2.9 nm, while F127 which has a distinctly smaller hydrophobic PO domain with a bending structure in the micelles successfully results in sub-2 nm PtM (M = Ru, Ir, Rh, Pd) nanoclusters in OMC. This well indicates that the nanocluster size is largely decided by the volume of the hydrophobic segment of the surfactant to which the metallic precursor is linked. The smaller the volume, the fewer the precursor molecules are adsorbed, and the smaller the alloy nanoclusters. In the electrocatalytic methanol oxidation reaction, the mass activity of PtRu-1.6/OMC with 1.6 nm PtRu clusters at 0.87 V reaches 1.07 A mgPt-1, which is 2.9 times that of commercial PtRu/C with an average alloy size of 2.7 nm. In principle, a wide range of ultrafine metallic clusters embedded in OMC can be prepared via this route for various applications.

Enhanced catalytic performance of RuNi alloy nanoclusters toward hydrolytic dehydrogenation of NH3BH3

Developing efficient and economical catalysts for ammonia borane (AB, NH3BH3) hydrolysis is of great significance in hydrogen generation. In this article, we support RuM (M = Fe, Co, Ni, Cu) alloys on graphene-doped porous g-C3N4 (named as g-C3N4-rGO) through an adsorption-chemical reduction procedure. Specifically, the Ru0.8Ni0.2 nanoclusters (NCs)-based heterogeneous catalysts exhibit higher catalytic activity toward the hydrolytic dehydrogenation of AB than the others. Catalyzed by Ru0.8Ni0.2/g-C3N4-rGO, the turnover frequency (TOF) reaches 905.0 min−1 in alkaline solution at 303 K, and the apparent activation energy (Ea) lowers to 27.2 kJ mol−1. The outstanding catalytic performance are originated from the highly dispersed RuNi NCs with a mean size of 1.40 nm, the fascinating alloy effect, as well as the unique geometric structure and heteroatomic groups of the g-C3N4-rGO composites. DFT calculation results further confirm that the alloy effect enhances the dissociation of H2O and hydrogen formation in AB hydrolysis, thus accelerating reaction rate. The facile fabrication strategy, reasonable cost-efficiency and exciting catalytic behavior endow the optimal catalysts promising potential in the field of hydrogen energy.

Natural plant compounds in synthesis and luminescence modulation of metal nanoclusters: Toward sustainable nanoprobes for sensing and bioimaging

Luminescent metal nanoclusters (LMNCs) with a diameter of less than 3 nm have fascinated scientific community in the past two decades for facile synthesis, ultra-small size, and tunable optical properties. For the synthesis and luminescence modulation of LMNCs, the plant kingdom provides a great deal of natural compounds, including various polyphenols, carbohydrates, and proteins. Because of the cost-effective, sustainable, and hypo-allergenic features of the plant compounds, they are preferred over both synthetic chemicals and biomolecules isolated from animals and microorganisms for synthesis, modification, and application of LMNCs. In this review, we first highlighted recent advances in the use of natural plant compounds for the preparation of LMNCs including gold, silver, copper, and alloy nanoclusters. Moreover, we discussed how the plant compounds modulated the luminescence properties of pre-synthesized LMNCs. Furthermore, the application of plant compounds-capped LMNCs in metal ions sensing, pesticide detection, biomarkers analysis, and bioimaging was surveyed. Finally, we briefly discussed the challenging issues and future perspectives in the field of plant compounds-capped LMNCs. This review demonstrates the critical role of natural plant compounds in the synthesis, luminescence modulation, and application of LMNCs, and is expected to offer inspiration for the further design and practical use of LMNCs.

A two-step optimization approach for structures investigation of Pd-Ir bimetallic nanoclusters

The structures of nanoalloys are crucial for understanding their catalytic performance because the stable structures can affect the activity and selectivity of nanocatalysts. Therefore, investigating the stable structures of nanoalloys is important to understand their catalytic activities. In this article, a two-step optimization approach by combining a basin hoping genetic algorithm (BHGA) and DFT calculation is employed to investigate the structural stability of Pd-Ir alloy nanoclusters. Different compositions (Pd and Ir atoms proportion) and different initial configurations of 38-atom Pd-Ir alloys are considered. The combination of BHGA and DFT method can effectively find the stable structures of truncated octahedral (TO) configurations for 38-atom Pd-Ir alloys with high accuracy and low time complexity. Furthermore, the formation energy and bond energy of Pd-Ir clusters are calculated and analyzed, the results show the bond strength follows Pd-Pd > Pd-Ir > Ir-Ir. The most stable configuration is Pd6Ir32 with all the core sites are occupied by Pd, which shows better electrochemical performance.

Burst release of antibacterial clusters from gold-silver nanoboxes triggered by carboxylates modulating electron compensation effect

Nanoalloys have been well attracted due to their unique physiochemical and optical properties. Although some nanoalloys are known to remain stable in complex biological environment because of the electron compensation effect (ECE), the effective modulation of ECE has yet to be explored. Here, we have demonstrated that the ECE can be modulated after adsorption of carboxylate on gold silver nanoboxes (GSNBs), accompanied with the release of alloy nanoclusters, as supported by X-ray photoelectron spectroscopy and the electron density difference calculation. Moreover, the modulation efficiency is dependent on the pH of solution and the number of carboxylate groups. Using citrate as a representative, about 80 % silver components of GSNBs can be oxidized and released within 30 min in the presence of H2O2, producing highly-efficient antibacterial alloy clusters for both in vitro and in vivo applications. These results may offer a deep insight into modulation of intermetallic electron transfer of nanoalloys to develop new and effective antibacterial strategies.

Synthesis of Cu@Pt‐Pd Ternary Metallic Composites for Efficient Electrocatalysis of Methanol

AbstractAn electrochemical preparation method of Cu@Pt‐Pd ternary metallic composite, which is used as excellent catalytic materials to oxide methanol under alkaline conditions, is reported in this work. Cu polyhedron as nuclei and Pt‐Pd alloy nanoclusters as shells of Cu@Pt‐Pd are proved by X‐ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The activities of composite materials are examined by linear sweep voltammetry, cyclic voltammetry, and chronoamperometry. The catalytic activity is investigated by modulating metal element proportion of Pt and Pd. The highest mass activity of Cu@Pt11.3Pd10.1 is 2387 mA mgPt+Pd−1 for methanol oxidation reaction. The mass activity of Cu@Pt11.3Pd10.1 is 3.42 folds relative to Pt/C catalysts. Compared with Pt/C catalysts, Cu@Pt‐Pd composites have higher CO resistance. This enhanced catalytic performance is closely related to its alloy structure through ligand and strain effects.

Combined synthesis of interconvertible Au11Cd and Au26Cd5 for photocatalytic oxidations involving singlet oxygen

A novel Au11Cd nanocluster was synthesized by developing a combined method and controlling the kinetics, and another Au26Cd5 nanocluster was also obtained after the conditions were changed in the same reaction, which could transfer to Au11Cd in a two-way style. Both alloy nanoclusters can photocatalyze the production of singlet oxygen (1O2) and exhibit enhanced efficiencies in photocatalyzing two kinds of organic oxidations involving singlet oxygen compared with their non-alloyed mother nanoclusters, indicating that the Cd-doping might be an efficient way to enhance the photocatalysis performance of gold nanoclusters and metal nanoclusters are promising photocatalysts for organic oxidation involving singlet oxygen.