Platinum Oxide Nanoparticles for Electrochemical Hydrogen Evolution: Influence of Platinum Valence State.

Electrochemical hydrogen generation is a rising prospect for future renewable energy storage and conversion. Platinum remains a leading choice of catalyst, but because of its high cost and low natural abundance, it is critical to optimize its use. In the present study, platinum oxide nanoparticles of approximately 2 nm in diameter are deposited on carbon nitride (C3N4) nanosheets by thermal refluxing of C3N4 and PtCl2 or PtCl4 in water. These nanoparticles exhibit apparent electrocatalytic activity toward the hydrogen evolution reaction (HER) in acid. Interestingly, the HER activity increases with increasing Pt4+ concentration in the nanoparticles, and the optimized catalyst even outperforms commercial Pt/C, exhibiting an overpotential of only -7.7 mV to reach the current density of 10 mA cm-2 and a Tafel slope of -26.3 mV dec-1 . The results from this study suggest that the future design of platinum oxide catalysts should strive to maximize the Pt4+ sites and minimize the formation of the less active Pt2+ species.

Antibacterial Activity of Nitrogen-Doped Carbon Dots Enhanced by Atomic Dispersion of Copper.

Antibiotic resistance is an imminent threat to human health, requiring the development of effective alternate antibacterial agents. One such alternative includes nanoparticle (photo)catalysts that are good at producing reactive oxygen species (ROS). Herein, we report the design and preparation of nitrogen-doped carbon dots functionalized with atomically dispersed copper centers by Cu-N coordination (Cu/NCD) that exhibit apparent antibacterial activity toward Gram-negative Escherichia coli (E. coli) under photoirradiation. The growth of E. coli cells is found to be markedly inhibited by Cu/NCD under 365 nm photoirradiation, whereas no apparent inhibition is observed in the dark or with the copper-free carbon dots alone. This is ascribed to the prolonged photoluminescence lifetime of Cu/NCD that facilitates the separation of photogenerated electron-hole pairs and ROS formation. The addition of tert-butyl alcohol is found to completely diminish the antimicrobial activity, suggesting that hydroxyl radicals are responsible for microbial death. Consistent results are obtained from fluorescence microscopic studies using CellROX green as the probe. Similar bactericidal behaviors are observed with Gram-positive Staphylococcus epidermidis (S. epidermidis). The copper content within the carbon material is optimized at a low loading of 1.09 wt %, reducing the possibility of toxic copper-ion leaching. Results from this study highlight the significance of carbon-based nanocomposites with isolated metal species as potent antimicrobial reagents.

Graphene Oxide Quantum Dot-Based Functional Nanomaterials for Effective Antimicrobial Applications.

Conventional ß-lactam antibiotics are resisted by bacteria at an increasing rate, prompting studies into the development of alternate antibiotic agents. In this personal account, we summarize recent progress in the design and engineering of graphene oxide quantum dot-based nanomaterials as potent antimicrobial agents. Specifically, we examine the impacts of chemical reduction on the antimicrobial activity of graphene oxide quantum dots, and enhancement of the bactericidal performance by the formation of nanocomposites with metal oxide nanoparticles, within the context of photodynamic generation of reactive oxygen species. A perspective is also included where the promises and challenges are highlighted in the development of high-performance antimicrobial agents based on graphene derivatives.

Impacts of ruthenium valence state on the electrocatalytic activity of ruthenium ion-complexed graphitic carbon nitride/reduced graphene oxide nanosheets towards hydrogen evolution reaction.

Design and engineering of effective electrode catalysts represents a critical first step for hydrogen production by electrochemical water splitting. Nanocomposites based on ruthenium atomically dispersed within a carbon scaffold have emerged as viable candidates. In the present study, ruthenium metal centers are atomically embedded within graphitic carbon nitride/reduced graphene oxide nanosheets by thermal refluxing. Subsequent chemical reduction/oxidation leads to ready manipulation of the ruthenium valence state, as evidenced in microscopic and spectroscopic measurements, and hence enhancement/diminishment of the electrocatalytic activity towards hydrogen evolution reaction in both acidic and alkaline media. This is largely ascribed to the increased/reduced contribution of the Ru valence electrons to the density of state near the Fermi level which dictates the binding and reduction of hydrogen. Results from this study highlight the significance of the valence state of metal centers in the manipulation and optimization of the catalytic performance of single atom catalysts.

Stable Cuprous Hydroxide Nanostructures by Organic Ligand Functionalization.

Copper compounds have been extensively investigated for diverse applications. However, studies of cuprous hydroxide (CuOH) have been scarce due to structural metastability. Herein, a facile, wet-chemistry procedure is reported for the preparation of stable CuOH nanostructures via deliberate functionalization with select organic ligands, such as acetylene and mercapto derivatives. The resulting nanostructures are found to exhibit a nanoribbon morphology consisting of small nanocrystals embedded within a largely amorphous nanosheet-like scaffold. The acetylene derivatives are found to anchor onto the CuOH forming CuC linkages, whereas CuS interfacial bonds are formed with the mercapto ligands. Effective electronic coupling occurs at the ligand-core interface in the former, in contrast to mostly non-conjugated interfacial bonds in the latter, as manifested in spectroscopic measurements and confirmed in theoretical studies based on first principles calculations. Notably, the acetylene-capped CuOH nanostructures exhibit markedly enhanced photodynamic activity in the inhibition of bacteria growth, as compared to the mercapto-capped counterparts due to a reduced material bandgap and effective photocatalytic generation of reactive oxygen species. Results from this study demonstrate that deliberate structural engineering with select organic ligands is an effective strategy in the stabilization and functionalization of CuOH nanostructures, a critical first step in exploring their diverse applications.

Ultrafast Preparation of Nonequilibrium FeNi Spinels by Magnetic Induction Heating for Unprecedented Oxygen Evolution Electrocatalysis.

Carbon-supported nanocomposites are attracting particular attention as high-performance, low-cost electrocatalysts for electrochemical water splitting. These are mostly prepared by pyrolysis and hydrothermal procedures that are time-consuming (from hours to days) and typically difficult to produce a nonequilibrium phase. Herein, for the first time ever, we exploit magnetic induction heating-quenching for ultrafast production of carbon-FeNi spinel oxide nanocomposites (within seconds), which exhibit an unprecedentedly high performance towards oxygen evolution reaction (OER), with an ultralow overpotential of only +260 mV to reach the high current density of 100 mA cm-2. Experimental and theoretical studies show that the rapid heating and quenching process (ca. 103 K s-1) impedes the Ni and Fe phase segregation and produces a Cl-rich surface, both contributing to the remarkable catalytic activity. Results from this study highlight the unique advantage of ultrafast heating/quenching in the structural engineering of functional nanocomposites to achieve high electrocatalytic performance towards important electrochemical reactions.

Photodynamic Activity of Graphene Oxide/Polyaniline/Manganese Oxide Ternary Composites toward Both Gram-Positive and Gram-Negative Bacteria.

Graphene derivatives have been attracting extensive interest as effective antimicrobial agents. In the present study, ternary nanocomposites are prepared based on graphene oxide quantum dots (GOQD), polyaniline (PANI), and manganese oxides. Because of the hydrophilic GOQD and PANI, the resulting GPM nanocomposites are readily dispersible in water and upon photoirradiation at 365 nm exhibit antimicrobial activity toward both Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus epidermidis (S. epidermidis). Notably, the nanocomposite with a high Mn2+ and Mn4+ content is found to be far more active than that with a predominant Mn3+ component, although both samples feature a similar elemental composition and average Mn valence state. The bactericidal activity is largely ascribed to the photocatalytic production of hydroxy radicals and photogenerated holes; both are known to exert oxidative stress on bacterial cells. Further antimicrobial contributions may arise from the strong affinity of the nanocomposites to the cell surfaces. These results suggest that the metal valence state may be a critical parameter in the design and engineering of high-performance antimicrobial agents based on metal oxide nanocomposites.

Oxygen Reduction Reaction Catalyzed by Carbon-Supported Platinum Few-Atom Clusters: Significant Enhancement by Doping of Atomic Cobalt.

Oxygen reduction reaction (ORR) plays an important role in dictating the performance of various electrochemical energy technologies. As platinum nanoparticles have served as the catalysts of choice towards ORR, minimizing the cost of the catalysts by diminishing the platinum nanoparticle size has become a critical route to advancing the technological development. Herein, first-principle calculations show that carbon-supported Pt9 clusters represent the threshold domain size, and the ORR activity can be significantly improved by doping of adjacent cobalt atoms. This is confirmed experimentally, where platinum and cobalt are dispersed in nitrogen-doped carbon nanowires in varied forms, single atoms, few-atom clusters, and nanoparticles, depending on the initial feeds. The sample consisting primarily of Pt2~7 clusters doped with atomic Co species exhibits the best mass activity among the series, with a current density of 4.16 A mgPt -1 at +0.85 V vs. RHE that is almost 50 times higher than that of commercial Pt/C.

Atomic Dispersion and Surface Enrichment of Palladium in Nitrogen-Doped Porous Carbon Cages Lead to High-Performance Electrocatalytic Reduction of Oxygen.

Metal-nitrogen-carbon (MNC) nanocomposites have been hailed as promising and efficient electrocatalysts toward oxygen reduction reaction (ORR), due to the formation of MNx coordination moieties. However, MNC hybrids are mostly prepared by pyrolysis of organic precursors along with select metal salts, where part of the MNx sites are inevitably buried in the carbon matrix. This limited accessibility compromises the electrocatalytic performance. Herein, we describe a wet-impregnation procedure by facile thermal refluxing, whereby palladium is atomically dispersed and enriched onto the surface of hollow, nitrogen-doped carbon cages (HNC) forming Pd-N coordination bonds. The obtained Pd-HNC nanocomposites exhibit an ORR activity in alkaline media markedly higher than that of metallic Pd nanoparticles, and the best sample even outperforms commercial Pt/C and relevant Pd-based catalysts reported in the literature. The results suggest that atomic dispersion and surface enrichment of palladium in a carbon matrix may serve as an effective strategy in the fabrication of high-performance ORR electrocatalysts.

Antimicrobial activity of graphene oxide quantum dots: impacts of chemical reduction.

Design and engineering of graphene-based functional nanomaterials for effective antimicrobial applications has been attracting extensive interest. In the present study, graphene oxide quantum dots (GOQDs) were prepared by chemical exfoliation of carbon fibers and exhibited apparent antimicrobial activity. Transmission electron microscopic measurements showed that the lateral length ranged from a few tens to a few hundred nanometers. Upon reduction by sodium borohydride, whereas the UV-vis absorption profile remained largely unchanged, steady-state photoluminescence measurements exhibited a marked blue-shift and increase in intensity of the emission, due to (partial) removal of phenanthroline-like structural defects within the carbon skeletons. Consistent results were obtained in Raman and time-resolved photoluminescence measurements. Interestingly, the samples exhibited apparent, but clearly different, antimicrobial activity against Staphylococcus epidermidis cells. In the dark and under photoirradiation (400 nm), the as-produced GOQDs exhibited markedly higher cytotoxicity than the chemically reduced counterparts, likely because of (i) effective removal by NaBH4 reduction of redox-active phenanthroline-like moieties that interacted with the electron-transport chain of the bacterial cells, and (ii) diminished production of hydroxyl radicals that were potent bactericidal agents after chemical reduction as a result of increased conjugation within the carbon skeletons.

Nanocomposites Based on Ruthenium Nanoparticles Supported on Cobalt and Nitrogen-Codoped Graphene Nanosheets as Bifunctional Catalysts for Electrochemical Water Splitting.

Rational design and engineering of high-efficiency electrocatalysts toward overall water splitting is crucial for the development of hydrogen energy technology. Herein, a facile procedure is described for the preparation of effective bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), where ruthenium nanoparticles are supported on graphene nanosheets that are codoped with atomic cobalt and nitrogen by controlled pyrolysis of melamine-functionalized graphene oxide and metal ion precursors. The obtained nanocomposites (CoNG/Ru) exhibit a remarkable electrocatalytic activity toward both HER and OER in alkaline media, with a respective overpotential of only -15 and +350 mV to reach the current density of 10 mA cm-2, which is much better than the monometallic counterparts and relevant catalysts in the literature. With CoNG/Ru as bifunctional catalysts for overall water splitting in a two-electrode system, a low potential of 1.58 V is needed to reach the current density of 10 mA cm-2, which is even better than that with commercial Pt/C and RuO2 catalysts. This is ascribed to the synergistic interactions between the metal species by metal-metal charge transfer. These results highlight the significance of exploiting the electronic interactions between metal species in carbon-based nanocomposites to develop bifunctional catalysts for electrochemical energy technologies.