Photocatalytic degradation of methyl blue dye with H2O2 sensing.

A condensation polymer (urea-formaldehyde resin) passivated ZnO nanoparticles were used as an efficient photocatalyst for methyl blue degradation in the presence of H2O2 involving a Fenton-like reaction. The formation of OH˙ radicals were attributed to the pivotal factor for the degradation process. The method was easy and recyclable. The dose of photocatalyst, initial dye concentration, pH variation, variations of the composition of the photocatalyst, and the effect of scavengers were gauged. The degraded product was highly fluorescent and fluorometric detection of H2O2 was achieved along with a colorimetric recognition pathway. No other dye could be degraded under similar experimental conditions, implying the novel utility of methyl blue for environmental remediation.

Role of transition metals in coinage metal nanoclusters for the remediation of toxic dyes in aqueous systems.

A difficult issue in chemistry and materials science is to create metal compounds with well-defined components. Metal nanoclusters, particularly those of coinage groups (Cu, Ag, and Au), have received considerable research interest in recent years owing to the availability of atomic-level precision via joint experimental and theoretical methods, thus revealing the mechanisms in diverse nano-catalysts and functional materials. The textile sector significantly contributes to wastewater containing pollutants such as dyes and chemical substances. Textile and fabric manufacturing account for about 7 × 105 tons of wastewater annually. Approximately one thousand tons of dyes used in textile processing and finishing has been recorded as being discharged into natural streams and water bodies. Owing to the widespread environmental concerns, research has been conducted to develop absorbents that are capable of removing contaminants and heavy metals from water bodies using low-cost technology. Considering this idea, we reviewed coinage metal nanoclusters for azo and cationic dye degradation. Fluorometric and colorimetric techniques are used for dye degradation using coinage metal nanoclusters. Few reports are available on dye degradation using silver nanoclusters; and some of them are discussed in detailed herein to demonstrate the synergistic effect of gold and silver in dye degradation. Mostly, the Rhodamine B dye is degraded using coinage metals. Silver nanoclusters take less time for degradation than gold and copper nanoclusters. Mostly, H2O2 is used for degradation in gold nanoclusters. Still, all coinage metal nanoclusters have been used for the degradation due to suitable HOMO-LUMO gap, and the adsorption of a dye onto the surface of the catalyst results in the exchange of electrons and holes, which leads to the oxidation and reduction of the adsorbed dye molecule. Compared to other coinage metal nanoclusters, Ag/g-C3N4 nanoclusters displayed an excellent degradation rate constant with the dye Rhodamine B (0.0332 min-1). The behavior of doping transition metals in coinage metal nanoclusters is also reviewed herein. In addition, we discuss the mechanistic grounds for degradation, the fate of metal nanoclusters, anti-bacterial activity of nanoclusters, toxicity of dyes, and sensing of dyes.

Highly fluorescent quinone-capped silver hydrosol for environmental remediation and sensing applications.

A metal-enhanced fluorescence was achieved from in situ-generated Ag0 nanoparticles in the proximity of 2-hydroxy benzaldehyde (2HB). Such nanoparticles eliminated methyl blue (MB) dye from water exclusively in the presence of Zn2+ and were proven to be an efficient adsorbent for environmental remediation (maximum uptake capacity 1065 mg·g-1). Ag was zero valent in the absorbent, while Zn2+ was in Zn(OH)2 form. Fe3+ brought back MB in the aqueous medium due to the strong interaction of MB with Fe3+ and the regeneration of blue color helped to design a selective and sensitive Fe3+ sensing platform colorimetrically (linear detection range 10-4-10-6 M; linear detection limit 10-6 M). The silver nanoparticle-induced metal-enhanced fluorescence was quenched efficiently with MB. Pb2+ restored the quenched fluorescence by removing MB from the proximity of the metalized surface of silver, and Pb2+ sensing was performed fluorometrically (linear detection range; 10-5-5 × 10-8 M limit of detection 5 × 10-8 M). Iron and lead were also estimated in a variety of natural water sources, including rainfall, drinking water from taps, and water from the Ganga River via spiking method.

Natural Kaolin: Sustainable Technology for the Instantaneous and Energy-Neutral Recycling of Anthropogenic Mercury Emissions.

Kaolin, a natural and inexpensive clay mineral, is ubiquitous in soil, dirt, and airborne particles. Amongst four commonly available clay minerals, kaolin, as a result of its layered structure, is the most efficient natural gaseous Hg adsorbent to date (Langmuir maximum adsorption capacity Qm =574.08 µg g-1 and Freundlich Qm =756.49 µg g-1 ). The Hg uptake proceeds by homogeneous monolayer and heterogeneous processes. Hg physisorption on kaolin occurs in the dark, yet the adsorption rate is enhanced upon irradiation. The effects of several metal complexes, salts, halides and solvents on the Hg uptake were examined. The addition of CuCl2 particles leads to a significant enhancement of the Hg uptake capacity (>30 times) within second timescales and without irradiation. The physisorption with kaolin is switched to chemisorption upon the addition of CuCl2 to kaolin. This process is entirely reversible upon the addition of Zn/Sn granules at room temperature without any added energy. However, the investment of a small amount of renewable energy can speed up the process. This technology demonstrates the facile and efficient capture and recycling of elemental Hg0 from air. A wide range of metal particles and diverse physicochemical processes, which include the microphysics of nucleation, are herein examined to explore the potential reaction mechanism by using a suite of complementary analytical techniques. These new mechanistic insights open a new era of energy-neutral environmental remediation based on natural soil/airborne particles.

Novel Technology for the Removal of Brilliant Green from Water: Influence of Post-Oxidation, Environmental Conditions, and Capping.

Chemical dyes are used in a wide range of anthropogenic activities and are generally not biodegradable. Hence, sustainable recycling processes are needed to avoid their accumulation in the environment. A one-step synthesis of Fecore-maghemiteshell (Fe-MM) for facile, instantaneous, cost-effective, sustainable, and efficient removal of brilliant green (BG) dye from water has been reported here. The homogenous and monolayer type of adsorption is, to our knowledge, the most efficient, with a maximum uptake capacity of 1000 mg·g-1, for BG on Fe-MM. This adsorbent was shown to be efficient in occurring in time-scales of seconds and to be readily recyclable (ca. 91%). As iron/iron oxide possesses magnetic behavior, a strong magnet could be used to separate Fe-MM coated with BG. Thus, the recycling process required a minimum amount of energy. Capping Fe-MM by hydrophilic clay minerals further enhanced the BG uptake capacity, by reducing unwanted aggregation. Interestingly, capping the adsorbent by hydrophobic plastic (low-density polyethylene) had a completely inverse effect on clay minerals. BG removal using this method is found to be quite selective among the five common industrial dyes tested in this study. To shed light on the life cycle analysis of the composite in the environment, the influence of selected physicochemical factors (T, pH, hν, O3, and NO2) was examined, along with four types of water samples (melted snow, rain, river, and tap water). To evaluate the potential limitations of this technique, because of likely competitive reactions with metal ion contaminants in aquatic systems, additional experiments with 13 metal ions were performed. To decipher the adsorption mechanism, we deployed four reducing agents (NaBH4, hydrazine, LiAlH4, and polyphenols in green tea) and NaBH4, exclusively, favored the generation of an efficient adsorbent via aerial oxidation. The drift of electron density from electron-rich Fecore to maghemite shells was attributed to be responsible for the electrostatic adsorption of N+ in BG toward Fe-MM. This technology is deemed to be environmentally sustainable in environmental remediation, namely, in waste management protocol.

Author Correction: Fast, Cost-effective and Energy Efficient Mercury Removal-Recycling Technology.

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Fast, Cost-effective and Energy Efficient Mercury Removal-Recycling Technology.

We herein present a novel and sustainable technology for mercury recycling, with the maximum observed uptake capacity. Facile synthesis of the most efficient (~1.9 gg-1) nano-trap, made of montmorillonite-Fe-iron oxides, was performed to instantaneously remove mercury(II) ions from water. Elemental Hg was recovered from the adduct, by employing Fe granules, at ambient conditions. Varied pHs and elevated temperatures further enhanced this already highly efficient recycling process. The reduction of Hg(II) to Hg(I) by the nano trap and Hg(I) to Hg(0) by Fe granules are the main driving forces behind the recycling process. Facile sustainable recycling of the nano-trap and Fe granules require no additional energy. We have further developed a recyclable model for Hg nano-trap, which is inexpensive (<$5 CAD), and can remove mercury in a few seconds. This technology has multiple applications, including in the communities exposed to mercury contamination.

Fluorescence enhancement via varied long-chain thiol stabilized gold nanoparticles: A study of far-field effect.

Metal enhanced fluorescence of carbon dots has been reported in aqueous solution. Moderately fluorescing carbon dots (λex=360nm and λem=440nm) of 6-8nm diameters (CDA) have been synthesized from freshly prepared aqueous ascorbic acid solution under modified hydrothermal treatment. The CDA fluorescence is quenched at the close proximity with gold nanoparticles (AuNPs). Here, a substrate specific near-field electric field distribution is pronounced. Anticipating distance dependent fluorescence enhancement phenomenon, long-chain aliphatic thiol capped AuNPs are introduced to improve fluorescence of moderately fluorescing CDAs. The long-chain aliphatic thiols act as spacers between CDA and AuNP. Interestingly, the fluorescence of CDA is observed to be enhanced successively as the chain lengths of aliphatic thiols are increased. Fluorescing CDA, upon excitation, transfers energy to the nearby AuNP and a plasmon is induced. This plasmon radiates in the far-field resulting in fluorescence enhancement of CDAs. Such an interesting enhancement in emission with metallic gold is termed as gold enhanced fluorescence. This far-field effect for fluorescence enhancement of CDA particles becomes a general consensus in solution with varied long-chain aliphatic amine ligand capped silver nanoparticles (AgNPs). Finally, consequence of far-field effect of fluorescence enhancement has been observed while derivatized AuNP and AgNP are introduced into the CDA solution simultaneously which is described as reinforced fluorescence enhancement due to coupled plasmonic radiation.

Purely Inorganic Highly Efficient Ice Nucleating Particle.

To evaluate the role of atmospheric heterogeneous reactions on the ice nucleation ability of airborne dust particles, we investigated the systematic study of ice nucleation microphysics with a suite of atmospherically relevant metals (10), halides (4), and oxyhalides (2). Within a minute, a kaolin-iron oxide composite (KaFe) showed efficient reactions with aqueous mercury salts. Among the different mercury salts tested, only HgCl2 reacting with KaFe generated HgKaFe, a highly efficient ice nucleating particle (HEIN). When added to water, HgKaFe caused water to freeze at much warmer temperatures, within a narrow range of -6.6 to -4.7 °C. Using a suite of optical spectroscopy, mass spectrometry, and microscopy techniques, we performed various experiments to decipher the physical and chemical properties of surface and bulk. KaFe was identified as a mixture of different iron oxides, namely, goethite, hematite, magnetite, and ε-Fe2O3, with kaolin. In HgKaFe, HgCl2 was reduced to Hg2Cl2 and iron was predominantly in maghemite form. Reduction of Fe2+ by NaBH4, followed by aerial oxidation, helped KaFe to be an exact precursor for the synthesis of HEIN HgKaFe. Kaolin served as a template for synthesizing iron oxide, opposing unwanted aggregation. No other metal or metal halide was found to have more efficient nucleating particles than HgCl2 with KaFe composite. The chelation of Hg(II) hindered the formation of HEIN. This study is useful for investigating the role of morphology and how inorganic chemical reactions on the surface of dust change morphology and thus ice nucleation activity. The understanding of the fundamentals of what makes a particle to be a good ice nucleating particle is valuable to further understand and predict the amount and types of atmospheric ice nucleating particles.

Boron Precursor-Dependent Evolution of Differently Emitting Carbon Dots.

Attention has been directed toward electron-deficient boron doping in carbon dots (CDs) with the expectation of revealing new photophysical aspects in accordance with varying amounts of boron content. It has been emphatically shown that boron uptake in CDs varies with different boron precursors evolving altered emissive CDs. Boron doping in CDs causes definite surface defect due to the generation of electron-deficient states. Modified hydrothermal treatment of a mixture of ascorbic acid (AA) and different boron precursor compounds (borax/boric acid/sodium borate/sodium borohydride) produces different kinds of boron-doped CDs (BCDs). These BCDs (<6 nm) differ in size, emission maxima (∼15 nm), and fluorescence intensity but carry unchanged excitation maxima (365 nm). These differences are related to the nature of boron precursor compounds. The most fluorescing BCD (quantum yield ≈ 5%) is identified from the borax-mediated reaction and is used for the detection of Fe(III) on a nanomolar level in water via the fluorescence "Turn Off" phenomenon. Again, Fe(III)-infested CD solution regains its lost fluorescence, with AA paving the way for nanomolar level AA detection from the same pot. The proposed method has been tactfully made interference free for the quantitative measure of Fe(III) and AA in real samples. Furthermore, new photophysical properties of the CDs with variable boron contents supplement information that is hitherto unknown. Theoretical calculations also justify the observed optical behavior of the as-synthesized BCDs. The calculations describe the variable amount of boron doping-related huge charge polarization within the carbon surface, leading to the formation of surface defects. Thus, subsequent electronic transition-related red shift in the absorption spectrum authenticates experimental findings.

A Segregated, Partially Oxidized, and Compact Ag10 Cluster within an Encapsulating DNA Host.

Silver clusters develop within DNA strands and become optical chromophores with diverse electronic spectra and wide-ranging emission intensities. These studies consider a specific cluster that absorbs at 400 nm, has low emission, and exclusively develops with single-stranded oligonucleotides. It is also a chameleon-like chromophore that can be transformed into different highly emissive fluorophores. We describe four characteristics of this species and conclude that it is highly oxidized yet also metallic. One, the cluster size was determined via electrospray ionization mass spectrometry. A common silver mass is measured with different oligonucleotides and thereby supports a Ag10 cluster. Two, the cluster charge was determined by mass spectrometry and Ag L3-edge X-ray absorption near-edge structure spectroscopy. Respectively, the conjugate mass and the integrated white-line intensity support a partially oxidized cluster with a +6 and +6.5 charge, respectively. Three, the cluster chirality was gauged by circular dichroism spectroscopy. This chirality changes with the length and sequence of its DNA hosts, and these studies identified a dispersed binding site with ∼20 nucleobases. Four, the structure of this complex was investigated via Ag K-edge extended X-ray absorption fine structure spectroscopy. A multishell fitting analysis identified three unique scattering environments with corresponding bond lengths, coordination numbers, and Debye-Waller factors for each. Collectively, these findings support the following conclusion: a Ag10(+6) cluster develops within a 20-nucleobase DNA binding site, and this complex segregates into a compact, metal-like silver core that weakly links to an encapsulating silver-DNA shell. We consider different models that account for silver-silver coordination within the core.

One pot synthesis of intriguing fluorescent carbon dots for sensing and live cell imaging.

We report a simple one-pot synthesis of highly fluorescent carbon dots (CDs) via modified hydrothermal (MHT) treatment of alkaline solution of dopamine and cysteine. These CDs (λex=320 nm, λem=390 nm, and quantum yield ∼ 5.1%) are of ∼ 2-3 nm in diameter. Further attempt of synthesizing CDs in some common water-miscible solvents ends up the fact that the MHT product from acetone medium is nonfluorescent. However, CDs, produced in aqueous medium, are so stable that they can be dried as a deliverable solid (WCD) without any alteration of fluorescing property if reversibly dispersed in water. Fluorescence of WCD is quenched selectively in acetone. Quenching occurs presumably due to the disruption of radiative recombination along with the hindrance in quantum confinement of the emissive energy traps to the particle surface. Successive quenching of fluorescence of WCD in different acetone concentration admixed in water paves the way to selective acetone sensing (LOD=8.75 × 10(-7) M). The synthesized CDs (in aqueous medium) are cytocompatible and are efficient fluorescent probe for cell imaging. Only living cells are recognized exclusively from fluorescence imaging leaving aside dead cells, while cells are treated with CDs.

Silver nanoparticle anchored carbon dots for improved sensing, catalytic and intriguing antimicrobial activity.

Fluorescent carbon dots (NSCDs) with a size of ∼5 nm (λex = 320 nm and λem = 386 nm) have been synthesized under reflux from an alkaline mixture of dopamine and cysteine. The synthesized NSCDs are hybridized with in situ generated silver nanoparticles (AgNPs) obtained by mixing AgNO3 at room temperature. NSCDs enrich the plasmonic bands of AgNPs due to the localized surface plasmon resonance (LSPR) effect. Further enrichment of plasmon band, depending on the acetone concentration, enables acetone sensing down to 8 × 10(-5) M admixed in 1 M water. Thus, acetone induced hybrid particles with a sharp plasmon band (λex = 410 nm) become a sulfide sensing platform. Furthermore, vacuum dried stable particles (with or without acetone) have been proven to be an excellent catalyst for selective reduction of cationic dyes and they exhibit intriguing antimicrobial activity. These two types of dry particle act differently, which enables us to distinguish their altered surface functionalization in terms of catalysis and bacterial growth.

Orange-red silver emitters for sensing application and bio-imaging.

Highly fluorescent Au(I)@Ag particles (emission maximum at 635 nm) have been obtained from a mixture of AgNO3, HAuCl4 and glutathione. Au(I)@Ag particles containing Ag2 and Ag3 clusters are produced when the reaction mixture is subjected to a modified hydrothermolysis (MHT) reaction. The silver clusters make the solution intensely fluorescent and the Au(I) moiety provides long term stability to the silver clusters by withdrawing electron density from the silver clusters. The vacuum-dried aqueous fluorescent solution leaves a yellow solid that exhibits higher emissive properties when re-dispersed in non-aqueous solvents. Fluorescent Au(I)@Ag particles have been found to be cytocompatible and efficient candidates for live cell imaging. Addition of S(2-) ions selectively and successively quenches the fluorescence of Au(I)@Ag particles without any significant interference from common anions. Thus, sensitive detection of S(2-) is possible with the fluorescent Au(i)@Ag particles in water and water-miscible non-aqueous solvents. Furthermore, Pb(ii) induced fluorescence enhancement of the solution containing Au(I)@Ag particles has been used to enable S(2-) detection free from interference by S2O3(2-) and I(-). The possibility of naked eye detection of S(2-) is also an additional advantage of this method as an orange color solution is developed exclusively with the S(2-) ion. Fluorometric determination of S(2-) has been rationalized for real environmental samples.

Ten-atom silver cluster signaling and tempering DNA hybridization.

Silver clusters with ∼10 atoms are molecules, and specific species develop within DNA strands. These molecular metals have sparsely organized electronic states with distinctive visible and near-infrared spectra that vary with cluster size, oxidation, and shape. These small molecules also act as DNA adducts and coordinate with their DNA hosts. We investigated these characteristics using a specific cluster-DNA conjugate with the goal of developing a sensitive and selective biosensor. The silver cluster has a single violet absorption band (λ(max) = 400 nm), and its single-stranded DNA host has two domains that stabilize this cluster and hybridize with target oligonucleotides. These target analytes transform the weakly emissive violet cluster to a new chromophore with blue-green absorption (λ(max) = 490 nm) and strong green emission (λ(max) = 550 nm). Our studies consider the synthesis, cluster size, and DNA structure of the precursor violet cluster-DNA complex. This species preferentially forms with relatively low amounts of Ag(+), high concentrations of the oxidizing agent O2, and DNA strands with ≳20 nucleotides. The resulting aqueous and gaseous forms of this chromophore have 10 silvers that coalesce into a single cluster. This molecule is not only a chromophore but also an adduct that coordinates multiple nucleobases. Large-scale DNA conformational changes are manifested in a 20% smaller hydrodynamic radius and disrupted nucleobase stacking. Multidentate coordination also stabilizes the single-stranded DNA and thereby inhibits hybridization with target complements. These observations suggest that the silver cluster-DNA conjugate acts like a molecular beacon but is distinguished because the cluster chromophore not only sensitively signals target analytes but also stringently discriminates against analogous competing analytes.

Imine (-CH=N-) brings selectivity for silver enhanced fluorescence.

Metal enhanced fluorescence (MEF) from organic molecules has been the focus of plasmonic/photonic research. In this regard, silver and gold particle stimulated fluorescence has received much attention. However, the involvement of small organic molecules in solution has not been accounted for in MEF. We have reported here that the aqueous alkaline solution of salicylaldehyde exhibits highly enhanced fluorescence at room temperature (λ(em) ∼ 420 nm, Stokes shift 120 nm, stability > a year) in the presence of Ag(I) or Au(III) after simple ageing for two days. The increased scattering cross-section of the in situ produced aggregated metal particles and the lightening rod effect of the metal aggregates that concentrate the electric field around the fluorophore (i.e., alkaline solutions of salicylaldehyde) are ascribed to such extraordinary fluorescence enhancement caused by Ag and Au particles. Finally, selective fluorescence enhancement due to silver particles alone has been made possible in the presence of ammonia or primary amines due to imine bond formation that eliminates Au enhanced fluorescence quantitatively. This finding allows us to design a highly selective Ag(I) sensor in the solution phase with a cheap and commercially available compound with LOD far below EPA-permissible levels. The imine induced selective silver enhanced fluorescence phenomenon becomes a general matter in our studies even with different Schiff bases.

DNA-Directed Fluorescence Switching of Silver Clusters.

Silver clusters with ≲30 atoms are molecules with diverse electronic spectra and wide-ranging emission intensities. Specific cluster chromophores form within DNA strands, and we consider a DNA scaffold that transforms a pair of silver clusters. This ~20-nucleotide strand has two components, a cluster domain (S1) that stabilizes silver clusters and a recognition site (S2) that hybridizes with complementary oligonucleotides (S2C). The single-stranded S1-S2 exclusively develops clusters with violet absorption and low emission. This conjugate hybridizes with S2C to form S1-S2:S2C, and the violet chromophore transforms to a fluorescent counterpart with λex ≈ 490 nm/λem ≈ 550 nm and with ~100-fold stronger emission. Our studies focus on both the S1 sequence and structure that direct this violet → blue-green cluster transformation. From the sequence perspective, C4X sequences with X = adenine, thymine, and/or guanine favor the blue-green cluster, and the specificity of the binding site depends on three factors: the number of C4X repeats, the identity of the X nucleobase, and the number of contiguous cytosines. A systematic series of oligonucleotides identified the optimal S1 sequence C4AC4T and discerned distinct roles for the adenine, thymine, and cytosines. From the structure perspective, two factors guide the conformation of the C4AC4T sequence: hybridization with the S2C complement and coordination by the cluster adduct. Spectroscopic and chromatographic studies show that the single-stranded C4AC4T is folded by its blue-green cluster adduct. We propose a structural model in which the two C4X motifs within C4AC4T are cross-linked by the encapsulated cluster. These studies suggest that the structures of the DNA host and the cluster adduct are interdependent.

Intriguing cysteine induced improvement of the emissive property of carbon dots with sensing applications.

A simple fluorometric technique has been adopted for cysteine (Cys) sensing in alkaline medium down to the nM level. The huge fluorescent signal of the solution is a consequence of fluorescent carbon dots (CDs) produced in situ from modified hydrothermal (MHT) reaction between Cys and dopamine (DA). It has been observed that the inherent fluorescence of DA is drastically quenched in alkaline solution. Cys can selectively rescue the fluorescence of DA. Thus, Cys determination in a straightforward way, but only to a micro molar (10(-7) M i.e. 0.1 µM) level is possible through such fluorescence enhancement. Sensitive Cys determination remains associated with the in situ generated CDs, but the external addition of pre-formed CDs to Cys solution fails miserably towards Cys detection. However, CDs prepared from the Cys-DA system in alkaline solution admirably increase the limit of detection (LOD) of Cys at least two orders higher (10(-9) M) than that observed without hydrothermal technique i.e., without CDs. This method finds applications for Cys determination in biological samples and pharmaceutical preparations.

Precursor salt assisted syntheses of high-index faceted concave hexagon and nanorod-like polyoxometalates.

This paper describes an effective method for a precursor salt assisted fabrication and reshaping of two different polyoxometalates [(NH4)2Cu(MoO4)2 (ACM) and Cu3(MoO4)2(OH)2 (CMOH)] into five distinctive shapes through straightforward and indirect routes. Explicit regulation of the structural arrangements of ACM and CMOH has been studied in detail with altered precursor salt concentration employing our laboratory developed modified hydrothermal (MHT) method. Morphologically different ACM 3D architectures are evolved with higher molybdate concentration, whereas 1D growth of CMOH is observed with increased copper concentration. Interesting morphological transformation of the products has been accomplished employing one precursor salt at a time without using any other foreign reagent. It has been proven that large ACMs become labile in the presence of incoming Cu(II) and NH4(+) ions of the precursor salts. A new strategy for the conversion of faceted ACMs (hexagonal plate, circular plate and hollow flower) to exclusive CMOH nanorods through a Cu(II) assisted reaction has been adopted. According to thermodynamic consideration, the synthesis of rare concave nanostructures with high index facet is still challenging due to their higher reactivity. In this study, concave hexagonal ACM with high index facet {hkl} has been successfully prepared for the first time from hexagonal ACM through simple etching with ammonium heptamolybdate (AHM), which is another precursor salt. Hexagonal ACM corrugates to a concave hexagon because of the higher reactivity of the {001} crystal plane than that of the {010} plane. It has been shown that high index facet exposed concave hexagonal ACM serves as a better catalyst for the photodegradation of dye than the other microstructures enclosed by low index facets.

Fabrication of superhydrophobic copper surface on various substrates for roll-off, self-cleaning, and water/oil separation.

Superhydrophobic surfaces prevent percolation of water droplets and thus render roll-off, self-cleaning, corrosion protection, etc., which find day-to-day and industrial applications. In this work, we developed a facile, cost-effective, and free-standing method for direct fabrication of copper nanoparticles to engender superhydrophobicity for various flat and irregular surfaces such as glass, transparency sheet (plastic), cotton wool, textile, and silicon substrates. The fabrication of as-prepared superhydrophobic surfaces was accomplished using a simple chemical reduction of copper acetate by hydrazine hydrate at room temperature. The surface morphological studies demonstrate that the as-prepared surfaces are rough and display superhydrophobic character on wetting due to generation of air pockets (The Cassie-Baxter state). Because of the low adhesion of water droplets on the as-prepared surfaces, the surfaces exhibited not only high water contact angle (164 ± 2°, 5 µL droplets) but also superb roll-off and self-cleaning properties. Superhydrophobic copper nanoparticle coated glass surface uniquely withstands water (10 min), mild alkali (5 min in saturated aqueous NaHCO3 of pH ≈ 9), acids (10 s in dilute HNO3, H2SO4 of pH ≈ 5) and thiol (10 s in neat 1-octanethiol) at room temperature (25-35 °C). Again as-prepared surface (cotton wool) was also found to be very effective for water-kerosene separation due to its superhydrophobic and oleophilic character. Additionally, the superhydrophobic copper nanoparticle (deposited on glass surface) was found to exhibit antibacterial activity against both Gram-negative and Gram-positive bacteria.