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The emerging promise of few-atom metal catalysts has driven the need for developing metal nanoclusters (NCs) with ultrasmall core size. However, the preparation of metal NCs with single-digit metallic atoms and atomic precision is a major challenge for materials chemists, particularly for Ag, where the structure of such NCs remains unknown. In this study, we developed a shape-controlled synthesis strategy based on an isomeric dithiol ligand to yield the smallest crystallized Ag NC to date: [Ag9(1,2-BDT)6]3– (1,2-BDT = 1,2-benzenedithiolate). The NC’s crystal structure reveals the self-assembly of two Ag square pyramids through preferential pyramidal vertex sharing of a single metallic Ag atom, while all other Ag atoms are incorporated in a motif with thiolate ligands, resulting in an elongated body-centered Ag9 skeleton. Steric hindrance and arrangement of the dithiolated ligands on the surface favor the formation of an anisotropic shape. Time-dependent density functional theory based calculations reproduce the experimental optical absorption features and identify the molecular orbitals responsible for the electronic transitions. Our findings will open new avenues for the design of novel single-digit metal NCs with directional self-assembled building blocks., An isomeric dithiol-based synthesis strategy is used to synthesize the smallest crystallized Ag nanocluster, [Ag9(1,2-BDT)6]3−. The single-digit cluster reveals novel bonding modes and building blocks, which include the self-assembly of two Ag square pyramids sharing a common vertex and six bidentate thiolate motifs.

Atomically precise coinage metal (Au, Ag, and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical, and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC [Cu32(PET)24H8Cl2](PPh4)2 coprotected by 2-phenylethanethiolate (PET), hydride, and chloride ligands. Its crystal structure comprises a rare bisquare antiprismatic Cu14H8 core, assembled by two square antiprisms by edge sharing, followed by hydride binding. The rod-shaped Cu14H8 core is clamped by two complex Cu7(PET)11Cl and two simple Cu2PET metal ligand frameworks, constructing the complete structure of Cu32 NC. The presence, number, and location of hydrides are established by combined experimental and density functional theory results. The electronic structure calculations show the cluster as a zero-free-electron system, reproduce well the measured optical absorption spectrum, and explain the main absorption features. Furthermore, the Cu32 cluster is found to be a highly active homogeneous catalyst for C-N bond formation in aniline carbonylation reactions at room temperature. We hope that new findings in this work will stimulate and expand the research on Cu and other active metal NCs.

Noble metal‐based multimetallic nanoparticles (NMMNs) have attracted great attention for their multifunctional and synergistic effects, which offer numerous catalytic applications. Combined experimental and theoretical studies have enabled formulation of various design principles for tuning the electrocatalytic performance through controlling size, composition, morphology, and crystal structure of the nanoparticles. Despite significant advancements in the field, the chemical synthesis of NMMNs with ideal characteristics for catalysis, including high activity, stability, product‐selectivity, and scalability is still challenging. This review provides an overview on structure‐based classification and the general synthesis of NMMN electrocatalysts. Furthermore, postsynthetic treatments, such as the removal of surfactants to optimize the activity, and utilization of NMMNs onto suitable support for practical electrocatalytic applications are highlighted. In the end, future direction and challenges associated with the electrocatalysis of NMMNs are covered., Intriguing surface and structural properties makes noble metal‐based multimetallic nanoparticles (NMMNs) efficient catalysts for a wide‐range of electrocatalytic applications. This review provides an overview of the general preparation of electrocatalysts using NMMNs, including synthesis of NMMNs with precise control, and practical issues for applying the nanoparticles to electrocatalytic reactions.

While there are numerous recent reports on doping of a ligand-protected noble metal nanocluster (e.g., Au and Ag) with another noble metal, non-noble metal (e.g., Cd) doping remains challenging. Here, we design a phosphine-assisted synthetic strategy and synthesize a Cd doped Ag nanocluster, Cd12Ag32(SePh)36 (SePh: selenophenolate), which exhibits characteristic UV–vis absorption features and rare near-infrared (NIR) photoluminescence at ∼1020 nm. The X-ray single crystal structure reveals an asymmetric two-shell Ag4@Ag24 metal kernel protected by four nonplanar Cd3Ag(SePh)9 metal–ligand frameworks. Furthermore, the electronic structure analysis shows that the cluster is a 20-electron “superatom” and density functional theory predicts that its chiral optical response is comparable to the well-known Au38(SR)24 cluster. Our synthetic approach will pave a new path for introducing other non-noble metals into noble metal nanoclusters for exploring their effect on optical and chemical properties.

Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. To date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric study of the reaction of glutathione (GSH) protected silver clusters in the presence of excess ligand, GSH, using isothermal titration calorimetry (ITC). We have studied Ag11(SG)7 and Ag32(SG)19 clusters and compared their reactivity with GSH protected silver nanoparticles (AgNPs) and silver ions. Clusters show intermediate reactivity toward excess ligand compared to nanoparticles and silver ions. Several control experiments were performed to understand the degradation mechanism of these silver clusters and nanoparticles. The effect of dissolved oxygen in the degradation process was studied in detail, and it was found that it did not have a significant role, although alternate pathways of degradation with the involvement of oxygen cannot be ruled out. Direct confirma...

Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [Pt2Ag23Cl7(PPh3)10]. Its crystal structure revealed the self-assembly of two Pt-centered Ag icosahedra through vertex sharing. Five bridging and two terminal chlorides and 10 PPh3 ligands were found to stabilize the cluster. Electronic structure simulations corroborated structural and optical characterization of the cluster and provided insights into the effect of the Pt dopants on the optical properties and stability of the cluster. Our study will open new avenues for designing novel self-assembled NCs using different elemental dopants.

Modulating the structure–property relationship in atomically precise nanoclusters (NCs) is vital for developing novel NC materials and advancing their applications. While promising biphasic ligand-exchange (LE) strategies have been developed primarily to attain novel NCs, understanding the mechanistic aspects involved in tuning the core and the ligand-shell of NCs in such biphasic processes is challenging. Here, we design a single phase LE process that enabled us to elucidate the mechanism of how a hollow NC (e.g., [Ag44(SR)30]4–, SR: thiolate) converts into a nonhollow NC (e.g., [Ag25(SR)18]−) and vice versa. Our study reveals that the complete LE of the hollow [Ag44(SPhF)30]4– NCs (SPhF: 4-fluorobenzenethiolate) with incoming 2,4-dimethylbenzenethiol (HSPhMe2) induced distortions in the Ag44 structure forming the nonhollow [Ag25(SPhMe2)18]− by a disproportionation mechanism, while the reverse reaction of [Ag25(SPhMe2)18]− with HSPhF prompted an unusual dimerization of Ag25, followed by a rearrangement s...

Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e., Ag13, unlike the common centered Ag13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag67 were comp...

The properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another, a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of atomically precise silver NCs, in a biphasic liquid-liquid system, which is particularly of interest because of its complete reversibility and ability to occur at room temperature. We explore this phenomenon in-depth using Ag35(SG)18 [SG = glutathionate] and Ag44(4-FTP)30 [4-FTP = 4-fluorothiophenol] as model systems. We show that the ligand-exchange conversion of Ag35(SG)18 into Ag44(4-FTP)30 is rapid (

Silver nanoparticles with an atomically precise molecular formula [Ag25(SR)18](-) (-SR: thiolate) are synthesized, and their single-crystal structure is determined. This synthesized nanocluster is the only silver nanoparticle that has a virtually identical analogue in gold, i.e., [Au25(SR)18](-), in terms of number of metal atoms, ligand count, superatom electronic configuration, and atomic arrangement. Furthermore, both [Ag25(SR)18](-) and its gold analogue share a number of features in their optical absorption spectra. This unprecedented molecular analogue in silver to mimic gold offers the first model nanoparticle platform to investigate the centuries-old problem of understanding the fundamental differences between silver and gold in terms of nobility, catalytic activity, and optical property.

The properties of Ag nanoclusters are not as well understood as those of their more precious Au cousins. However, a recent surge in the exploration of strategies to tune the physicochemical characteristics of Ag clusters addresses this imbalance, leading to new insights into their optical, luminescence, crystal habit, metal-core, ligand-shell, and environmental properties. In this Perspective, we provide an overview of the latest strategies along with a brief introduction of the theoretical framework necessary to understand the properties of silver nanoclusters and the basis for their tuning. The advances in cluster research and the future prospects presented in this Perspective will eventually guide the next large systematic study of nanoclusters, resulting in a single collection of data similar to the periodic table of elements.

The drawbacks of existing fluoride removal processes are due to low efficiencies and less mechanistic understanding of the process. The acid–base protolysis and surface complexation constants for fluoride and thermally activated nanogibbsite were investigated in this study for the first time. Fluoride adsorption on heat activated gibbsite nanoparticles (HGNP) was determined as a function of pH, concentration of background electrolyte and adsorbate loading. XRD evidenced the HGNP is in a transient state of the formation of χ-alumina as a poorly crystalline solid. An immense increase in surface area was obtained from 50 to 399 m2/g by the heat activation. Macroscopic data obtained from the batch experiments suggested an enhanced fluoride removal by HGNP with an adsorption maximum around pH 6. The adsorption quantified by the diffuse double layer surface complexation model indicated an inner sphere complexation mechanism at 0.526 mM of F with monodentate mononuclear complexes. An increase of fluoride concentration to 1.351 mM demonstrated a multilayer complex formation which was also confirmed by the isotherm data modeling with two distinct sorption maxima. XPS evidenced similar results showing two peaks at 684.7 and 688.5 eV for weak and strong bonded fluoride on HNGP surface. Fluoride adsorption maximum was reported as 4 × 10−6 mol/m2 based on Langmuir data fitting.

We report a one-step and high yield synthesis of a red-luminescent silver cluster with the molecular formula, Ag11(SG)7 (SG: glutathionate) via reduction of silver ions by sodium borohydride in the presence of the tripeptide, glutathione (GSH). The as-prepared cluster shows prominent absorption features at 485 and 625 nm in its UV-vis absorption spectrum. Aging of the as-prepared cluster solution led to the disappearance of the 625 nm peak, followed by broadening of the 485 nm peak to give three maxima at ?487, 437, and 393 nm in its absorption spectrum. These peaks remain unchanged even after polyacrylamide gel electrophoresis (PAGE), where a single band was observed confirming high purity of the cluster formed. Electrospray ionization mass spectrometry (ESI MS) reveal the composition of the cluster to be Ag11(SG)7 with multiple sodium attachments to the ligand to give -3 and -2 charged species. These compositions match well with their calculated isotope patterns. Extensive MS/MS was performed to understand the fragmentation. Potential atomic structures are discussed based on density functional theory calculations and comparisons for optical absorption spectra using Ag11(SCH3)7 as the model. Photoluminescence of this cluster was selectively quenched in the presence of Hg(II) and Cu(II) separately. Detection limit was found to be below their permissible limits in drinking water set by US EPA. Ag11(SR)7 cluster is reported for the first time. � 2014 American Chemical Society.

We report a facile and rapid (less than 15 min) synthesis of atomically precise, dithiol-protected, silver quantum cluster, Ag7(DMSA) 4 (DMSA: meso-2,3-dimercaptosuccinic acid), through a modified solid state route. The as-synthesized cluster exhibits molecular optical absorption features with a prominent ?max at ?500 nm. Composition of the cluster was confirmed using various spectroscopic and microscopic techniques such as electrospray ionization mass spectrometry (ESI MS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive analysis of X-rays (EDAX). Clusters supported on neutral alumina have been shown as better adsorbents for selective adsorption of cationic dyes (over anionic dyes) from water. This selectivity for cationic dyes was evaluated by zeta potential (?) measurements. The efficiency of clusters for removal of dyes is very high when compared to nanoparticles (NPs) protected with ligands (citrate and mercaptosuccinic acid (MSA)) possessing similar chemical structures as that of DMSA. The higher efficiency of clusters for the removal of dyes is attributed to their smaller size and large surface area compared to the NPs in addition to favorable electrostatic interactions between the clusters and cationic dyes. Adsorption of dyes (cationic and anionic) was enhanced when dye molecules contain hydrogen bond forming functional groups. Supported clusters have been reused up to five cycles without the loss of activity once the adsorbed dye is extracted using suitable solvents. � 2013 American Chemical Society.

We describe the degradation of chlorocarbons (CCl4, C 6H5CH2Cl and CHCl3) in solution at room temperature (27 � 4 �C) by the monolayer-protected silver quantum cluster, Ag9MSA7 (MSA: mercaptosuccinic acid) in the presence of isopropyl alcohol (IPA). The main degradation products were silver chloride and amorphous carbon. Benzyl chloride was less reactive towards clusters than CCl4 and CHCl3. Materials used in the reactions and the reaction products were characterized using several spectroscopic and microscopic tools such as ultraviolet-visible (UV/Vis) absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), photoluminescence spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), energy dispersive analysis of X-rays (EDAX) and scanning electron microscopy (SEM). We have shown that clusters are more efficient for the degradation of halocarbons than the corresponding monolayer-protected nanoparticles (Ag@MSA, particle diameter 15 � 5 nm) at a given time and temperature. The higher reactivity of clusters is attributed to their small size and large surface area. Clusters and nanoparticles were used for reactions in supported (on neutral alumina) and unsupported forms. A possible mechanism for the reaction has been postulated on the basis of experimental results. � 2013 The Royal Society of Chemistry.

The development of luminescent mercury sulfide quantum dots (HgS QDs) through the bio-mineralization process has remained unexplored. Herein, a simple, two-step route for the synthesis of HgS quantum dots in bovine serum albumin (BSA) is reported. The QDs are characterized by UV-vis spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, luminescence, Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), circular dichroism (CD), energy dispersive X-ray analysis (EDX), and picosecond-resolved optical spectroscopy. Formation of various sizes of QDs is observed by modifying the conditions suitably. The QDs also show tunable luminescence over the 680-800 nm spectral regions, with a quantum yield of 4-5%. The as-prepared QDs can serve as selective sensor materials for Hg(II) and Cu(II), based on selective luminescence quenching. The quenching mechanism is found to be based on Dexter energy transfer and photoinduced electron transfer for Hg(II) and Cu(II), respectively. The simple synthesis route of protein-capped HgS QDs would provide additional impetus to explore applications for these materials. Copyright � 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A highly luminescent freestanding film composed of the quantum cluster, Au 15, was prepared. We studied the utility of the material for specific metal ion detection. The sensitivity of the red emission of the cluster in the composite to Cu 2+ has been used to make a freestanding metal ion sensor, similar to pH paper. The luminescence of the film was stable when exposed to several other metal ions such as Hg 2+, As 3+, and As 5+. The composite film exhibited visual sensitivity to Cu 2+ up to 1 ppm, which is below the permissible limit (1.3 ppm) in drinking water set by the U.S. environmental protection agency (EPA). The specificity of the film for Cu 2+ sensing may be due to the reduction of Cu 2+ to Cu 1+/Cu 0 by the glutathione ligand or the Au 15 core. Extended stability of the luminescence of the film makes it useful for practical applications. � 2012 American Chemical Society.

The bottom-up assembly of nanoparticles into diverse ordered solids is a challenge because it requires nanoparticles, which are often quasi-spherical, to have interaction anisotropy akin to atoms and molecules. Typically, anisotropy has been introduced by changing the shape of the inorganic nanoparticle core. Here, we present the design, self-assembly, optical properties, and total structural determination of Ag29(BDT)12(TPP)4, an atomically precise tetravalent nanocluster (NC) (BDT, 1,3-benzenedithiol; TPP, triphenylphosphine). It features four unique tetrahedrally symmetrical binding surface sites facilitated by the supramolecular assembly of 12 BDT (wide footprint bidentate thiols) in the ligand shell. When each of these sites was selectively functionalized by a single phosphine ligand, particle stability, synthetic yield, and the propensity to self-assemble into macroscopic crystals increased. The solid crystallized NCs have a substantially narrowed optical band gap compared to that of the solution state, suggesting strong interparticle electronic coupling occurs in the solid state.

Reactivity of two different nanosystems of silver, namely nanoparticles and atomically precise clusters, toward 1D tellurium nanowires (NWs) was probed and compared with the reaction of silver ions. While the reaction of nanoparticles and ions led to silver telluride nanowires, a different reactivity was exhibited by clusters which resulted in silver islands at different positions on the Te NWs. These hybrid Ag nodule-decorated Te NWs are sensitive to temperature, and they transform to dumbbell-shaped silver-tipped Te NWs upon solution phase annealing. Differences in chemical reactivity of nanoparticles of two different size regimes with nanowires are demonstrated. Synthetic methods of this kind will be useful in creating complex nanostructures which are difficult to be made in the solution phase. � 2014 American Chemical Society.

Clusters composed of a 32 silver atom core, protected with thiolates of glutathione (GSH) and N-(2-mercaptopropionyl)glycine (MPGH), were synthesized by a solid-state route in milligram scale. They do not exhibit surface plasmon resonance unlike their larger sized nanoparticle analogues but show molecule-like features in absorption and luminescence spectra, falling in the visible window. The compositions Ag32SG19 (SG: thiolate of glutathione) and Ag32MPG19 (MPG: thiolate of MPGH) were identified from electrospray ionization mass spectrometry (ESI MS). Matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) was not successful for -SG protected clusters as reported before, but for Ag 32MPG19 a peak at 6.1 kDa was seen at a threshold laser intensity. This peak shifted to low mass region with increasing laser intensity due to systematic losses of Ag2S. Further confirmation of the composition Ag32SG19 was made using various studies such as XPS and EDAX. One-dimensional (1D) and two-dimensional (2D) NMR spectroscopic investigations of Ag32SG19 provided interesting spectral features which indicated the dominant -[SR-Ag-SR]- structural motif. This structural motif as the predominant entity is found for the first time in silver clusters. � The Royal Society of Chemistry 2013.

Application of nanoparticles (NPs) in environmental remediation such as water purification requires a detailed understanding of the mechanistic aspects of the interaction between the species involved. Here, an attempt was made to understand the chemistry of noble metal nanoparticle-pesticide interaction, as these nanosystems are being used extensively for water purification. Our model pesticide, chlorpyrifos (CP), belonging to the organophosphorothioate group, is shown to decompose to 3,5,6-trichloro-2-pyridinol (TCP) and diethyl thiophosphate at room temperature over Ag and Au NPs, in supported and unsupported forms. The degradation products were characterized by absorption spectroscopy and electrospray ionization mass spectrometry (ESI MS). These were further confirmed by ESI tandem mass spectrometry. The interaction of CP with NP surfaces was investigated using transmission electron microscopy, energy dispersive analysis of X-rays, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). XPS reveals no change in the oxidation state of silver after the degradation of CP. It is proposed that the degradation of CP proceeds through the formation of AgNP-S surface complex, which is confirmed by Raman spectroscopy. In this complex, the P-O bond cleaves to yield a stable aromatic species, TCP. The rate of degradation of CP increases with increase of temperature and pH. Complete degradation of 10 mL of 2 ppm CP solution is achieved in 3 h using 100 mg of supported Ag@citrate NPs on neutral alumina at room temperature at a loading of ?0.5 wt %. The effect of alumina and monolayer protection of NPs on the degradation of CP is also investigated. The rate of degradation of CP by Ag NPs is greater than that of Au NPs. The results have implications to the application of noble metal NPs for drinking water purification, as pesticide contamination is prevalent in many parts of the world. Study shows that supported Ag and Au NPs may be employed in sustainable environmental remediation, as they can be used at room temperature in aqueous solutions without the use of additional stimulus such as UV light. � 2012 American Chemical Society.

The efficacy and the interface interactions of fluoride on laterite were investigated using batch methods, under various ionic strengths, pH, fluoride loading and diverse spectroscopy along with surface complexation modeling. The laterite used in this study was rich in iron (40%) and aluminum (30%). Proton binding sites were characterized by potentiometric titrations yielding pH ZPC around pH 8.72. Adsorption of fluoride on laterite is strongly pH dependent showing a maximum adsorption at pH &lt, 5, though not affected by the electrolyte concentration. Experimental data were quantified with a 2pK generalized diffused layer model considering two different surface binding sites for both protons and anions, using reaction stoichiometries. Surface complexation modeling showed that both Fe and Al sites of the laterite surface contributes to fluoride adsorption via inner-sphere complexation forming monodentate mononuclear interaction with laterite. Fluoride adsorption followed the Freundlich isotherm, indicating multi-site complexation on the laterite surface. FT-IR spectroscopic data provides an evidence for increased hydrogen bonding, indicated by the broadening of the OH stretch features around 3300cm -1. � 2012 Elsevier B.V.

Herein, we report the emergence of multicolor photoluminescence in a mixed-valence manganite nanoparticle La0.67Sr0.33MnO 3 (LSMO NP) achieved through electronic structural modification of the nanoparticles upon functionalization with a biocompatible organic ligand, sodium tartrate. From UV-vis absorption, X-ray photoelectron spectroscopy (XPS), time-resolved photoluminescence study, and Raman spectroscopic measurements, it is revealed that ligand-to-metal charge transfer transitions from highest occupied molecular orbital (HOMO, centered in tartrate ligand) to lowest unoccupied molecular orbital (LUMO, centered in Mn3+/4+ of the NPs), and d-d transitions involving Jahn-Teller sensitive Mn3+ ions in the NPs plays the central role behind the origin of multiple photoluminescence from the ligand functionalized LSMO NPs. � 2012 American Chemical Society.

A one-pot synthesis of extremely stable, water-soluble Cu quantum clusters (QCs) capped with a model protein, bovine serum albumin (BSA), is reported. From matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, we assign the clusters to be composed of Cu 5 and Cu 13 cores. The QCs also show luminescence properties having excitation and emission maxima at 325 and 410 nm, respectively, with a quantum yield of 0.15, which are found to be different from that of protein alone in similar experimental conditions. The quenching of luminescence of the protein-capped Cu QCs in the presence of very low hydrogen peroxide concentration (approximately nanomolar, or less than part-per-billion) reflects the efficacy of the QCs as a potential sensing material in biological environments. Moreover, as-prepared Cu QCs can detect highly toxic Pb 2+ ions in water, even at the part-per-million level, without suffering any interference from other metal ions. � 2011 American Chemical Society.

We report the chemical interactions of unsupported and alumina-supported Ag 7 and Ag 8 clusters protected with MSA (mercaptosuccinic acid) with heavy metal ions Hg(II), Cd(II), and Pb(II) in water at different concentrations. The investigation was carried out to determine the feasibility of this interesting new class of materials called quantum clusters for water purification. These systems were studied using various spectroscopic and microscopic techniques such as ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, dynamic light scattering, zeta potential measurements, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and photoluminescence spectroscopy and in detail by X-ray photoelectron spectroscopy. We observed that the metal ions interact with both the silver atoms of the clusters and the functional groups of the capping agent (MSA). The mercuric ions were reduced to metallic mercury by both supported and unsupported clusters, due to the feasibility of the redox reaction, whereas no reduction was observed for Cd(II) and Pb(II). As a result of the interaction, the luminescence of the cluster is lost which can be used to sense Hg(II). At lower concentrations, the metal ions were chemically bonded to the carboxylate groups of MSA. Absence of reduction of Hg(II) at lower concentration is due to the chemical affinity of the ligands and the lower silver content per cluster compared to the number of carboxylate groups. � 2011 American Chemical Society.

In this work, we describe the use of silver nanoparticles of 9 ± 2 and 20 ± 5 nm core diameter, protected by mercaptosuccinic acid (MSA) and supported on activated alumina for the removal of mercuric ions present in contaminated waters, at room temperature (28 ± 1 °C). These two nanoparticle samples were prepared by using two Ag:MSA ratios 1:6 and 1:3, respectively, during synthesis and were loaded on alumina at 0.5 and 0.3% by weight. The mechanism of interaction of silver nanoparticles with Hg 2+ ions was studied using various analytical techniques such as ultraviolet–visible spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), dynamic light scattering (DLS), inductively coupled plasma-optical emission spectrometry (ICP-OES), energy dispersive analysis of X-rays (EDAX), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Interactions of the metal ion with the metal core, the surface head group and the monolayer functionality were investigated. A high removal ability of 0.8 g of mercury per gram of Ag@MSA was achieved in the case of 1:6 Ag@MSA. These two materials show better uptake capacity of Hg 2+ in the pH range of 5–6. The ease of synthesis of the nanomaterial by wet chemistry, capability to load on suitable substrates to create stable materials and affordable cost will make it possible to use this approach in field applications, especially for the treatment of Hg 2+ contaminated waters.

We have studied the chemical interaction of heavy metal ions such as Hg(II), Hg(I), Pb(II), and Cd(II) of various concentrations with naked and protected silver nanoparticles (Ag@citrate and Ag@MSA, respectively, where MSA is mercaptosuccinic acid). The particles were of 30 and 8 nm diameter, respectively. We observed that the metal ions interact with both the core of the nanoparticles and the functional groups of the capping agents. We study the effects of interaction using spectroscopic and microscopic techniques such as ultraviolet-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), and in detail by X-ray photoelectron spectroscopy (XPS). The Hg(II) and Hg(I) ions were reduced to metallic mercury by both of the nanoparticles, because of the feasibility of the redox reaction, whereas no reduction was observed for Cd(II) and Pb(II). The reduction of Hg(I) and Hg(II) ions was due to electrons supplied by the core silver atoms of the nanoparticles, at lower metal ion concentrations. At higher concentrations, the metal ions were chemically bonded to the carboxylate groups of the citrate and MSA. These heavy metal ions form stable sulfides. The presence of different sulfur species, such as oxidized sulfur, disulfides, and metal sulfides, was confirmed by XPS. � 2010 American Chemical Society.

We report the synthesis of luminescent AuAg alloy quantum clusters (QCs) in bovine serum albumin (BSA), for the first time, with experimentally determined atomic composition. Mixing of the as-synthesized protein-protected Au and Ag clusters resulted in the formation of alloy AuAg clusters within the BSA. Mass spectrometric analysis of the product of a 1:1 molar ratio reaction mixture of AuQC@BSA and AgQC@BSA suggested that the alloy clusters could be Au38-xAgx@BSA. Further analyses by standard techniques revealed that the alloy cluster core of ?1.2 nm diameter is composed of nearly zero valent Au and Ag atoms that exhibit distinctly different steady state and time resolved excited state luminescence profiles compared to the parent clusters. Tuning of the alloy composition was achieved by varying the molar ratio of the parent species in the reaction mixture and compositional changes were observed by mass spectrometry. In another approach, mixing of Au3+ ions with the as-synthesized AgQC@BSA also resulted in the formation of alloy clusters through galvanic exchange reactions. We believe that alloy clusters with the combined properties of the constituents in versatile protein templates would have potential applications in the future. The work presents interesting aspects of the reactivity of the protein-protected clusters. � 2012 The Royal Society of Chemistry.