Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols.

A strategy for the synthesis of a gold-based single-atom catalyst (SAC) via a one-step room temperature reduction of Au(III) salt and stabilization of Au(I) ions on nitrile-functionalized graphene (cyanographene; G-CN) is described. The graphene-supported G(CN)-Au catalyst exhibits a unique linear structure of the Au(I) active sites promoting a multistep mode of action in dehydrogenative coupling of organosilanes with alcohols under mild reaction conditions as proven by advanced XPS, XAFS, XANES, and EPR techniques along with DFT calculations. The linear structure being perfectly accessible toward the reactant molecules and the cyanographene-induced charge transfer resulting in the exclusive Au(I) valence state contribute to the superior efficiency of the emerging two-dimensional SAC. The developed G(CN)-Au SAC, despite its low metal loading (ca. 0.6 wt %), appear to be the most efficient catalyst for Si-H bond activation with a turnover frequency of up to 139,494 h-1 and high selectivities, significantly overcoming all reported homogeneous gold catalysts. Moreover, it can be easily prepared in a multigram batch scale, is recyclable, and works well toward more than 40 organosilanes. This work opens the door for applications of SACs with a linear structure of the active site for advanced catalytic applications.

Reduced Tiara-like Palladium Complex for Suzuki Cross-Coupling Reactions.

The design of highly active and structurally well-defined catalysts has become a crucial issue for heterogeneous catalysed reactions while reducing the amount of catalyst employed. Beside conventional synthetic routes, the employment of polynuclear transition metal complexes as catalysts or catalyst precursors has progressively intercepted a growing interest. These well-defined species promise to deliver catalytic systems where a strict control on the nuclearity allows to improve the catalytic performance while reducing the active phase loading. This study describes the development of a highly active and reusable palladium-based catalyst on alumina (Pd8 /Al2 O3 ) for Suzuki cross-coupling reactions. An octanuclear tiara-like palladium complex was selected as active phase precursor to give isolated Pd-clusters of ca. 1 nm in size on Al2 O3 . The catalyst was thoroughly characterised by several complementary techniques to assess its structural and chemical nature. The high specific activity of the catalyst has allowed to carry out the cross-coupling reaction in 30 min using only 0.12 mol % of Pd loading under very mild and green reaction conditions. Screening of various substrates and selectivity tests, combined with recycling and benchmarking experiments, have been used to highlight the great potentialities of this new Pd8 /Al2 O3 catalyst.

Nanotubular TiO x N y -Supported Ir Single Atoms and Clusters as Thin-Film Electrocatalysts for Oxygen Evolution in Acid Media.

A versatile approach to the production of cluster- and single atom-based thin-film electrode composites is presented. The developed TiO x N y -Ir catalyst was prepared from sputtered Ti-Ir alloy constituted of 0.8 ± 0.2 at % Ir in α-Ti solid solution. The Ti-Ir solid solution on the Ti metal foil substrate was anodically oxidized to form amorphous TiO2-Ir and later subjected to heat treatment in air and in ammonia to prepare the final catalyst. Detailed morphological, structural, compositional, and electrochemical characterization revealed a nanoporous film with Ir single atoms and clusters that are present throughout the entire film thickness and concentrated at the Ti/TiO x N y -Ir interface as a result of the anodic oxidation mechanism. The developed TiO x N y -Ir catalyst exhibits very high oxygen evolution reaction activity in 0.1 M HClO4, reaching 1460 A g-1 Ir at 1.6 V vs reference hydrogen electrode. The new preparation concept of single atom- and cluster-based thin-film catalysts has wide potential applications in electrocatalysis and beyond. In the present paper, a detailed description of the new and unique method and a high-performance thin film catalyst are provided along with directions for the future development of high-performance cluster and single-atom catalysts prepared from solid solutions.

Easy and Versatile Synthesis of Bulk Quantities of Highly Enriched 13C-Graphene Materials for Biological and Safety Applications.

The preparation of bulk quantities of 13C-labeled graphene materials is relevant for basic investigations and for practical applications. In addition, 13C-labeled graphene materials can be very useful in biological and environmental studies, as they may allow the detection of graphene or its derivatives in cells or organs. In this paper, we describe the synthesis of 13C-labeled graphene materials (few-layer graphene, FLG, and graphene oxide, GO) on a tens of mg scale, starting from 13C-labeled methane to afford carbon fibers, followed by liquid-phase exfoliation (FLG) or oxidation (GO). The materials have been characterized by several analytical and microscopic techniques, including Raman and nuclear magnetic resonance spectroscopies, thermogravimetric analysis, X-ray photoelectron spectroscopy, and X-ray powder diffraction. As a proof of concept, the distribution of the title compounds in cells has been investigated. In fact, the analysis of the 13C/12C ratio with isotope ratio mass spectrometry (IRMS) allows the detection and quantification of very small amounts of material in cells or biological compartments with high selectivity, even when the material has been degraded. During the treatment of 13C-labeled FLG with HepG2 cells, 4.1% of the applied dose was found in the mitochondrial fraction, while 4.9% ended up in the nuclear fraction. The rest of the dose did not enter into the cell and remained in the plasma membrane or in the culture media.

Electrochemical nitrogen reduction: recent progress and prospects.

Ammonia is one of the most useful chemicals for the fertilizer industry and is also promising as an important energy carrier for fuel cell application, and is currently mostly produced by the traditional Haber-Bosch process under high temperature and pressure conditions. This energy-intensive process is detrimental to the environment due to the dependence on fossil fuels and the emission of significant greenhouse gases (such as CO2). Ammonia production via the electrochemical nitrogen reduction reaction (ENRR) has been recognized as a green sustainable alternative to the Haber-Bosch process in recent years. Current ENRR research mainly focuses on the catalyst for ammonia selective production and the enhancement of faradaic efficiency at high current density; however, these have not been explored well due to the unavailability of highly efficient and cheap catalysts. Herein, this review provides information on the ENRR process along with (i) theoretical background, (ii) experimental methodology of the electrocatalytic process and (iii) computational screening of promising catalysts. The impact of active sites and defects on the activity, selectivity, and stability of the catalysts is deeply understood. Furthermore, we demonstrate the mechanistic understanding of the ENRR process on the surface of catalysts, with the aim of boosting the improvement of the ENRR activities. The ammonia detection methods are also summarized along with thorough discussion of control experiments. Finally, this review highlights prevailing problems in existing ENRR methods of ammonia production along with technical advancements proposed to address these issues and concludes with comments on opportunities and future directions of the ENRR process.

Modulation of N

The efficient copolymerisation of functionalised olefins with alkenes continues to offer considerable challenges to catalyst design. Based on recent work using palladium complexes containing a dissymmetric N^N'-bidentate pyridyl-PYA ligand (PYA = pyridylidene amide), which showed a high propensity to insert methyl acrylate, we have here modified this catalyst structure by inserting shielding groups either into the pyridyl fragment, or the PYA unit, or both to avoid fast ß-hydrogen elimination. While a phenyl substituent at the pyridyl side impedes catalytic activity completely and leads to an off-cycle cyclometallation, the introduction of an ortho-methyl group on the PYA side of the N^N'-ligand was more prolific and doubled the catalytic productivity. Mechanistic investigations with this ligand system indicated the stabilisation of a 4-membered metallacycle intermediate at room temperature, which has previously been postulated and detected only at 173 K, but never observed at ambient temperature so far. This intermediate was characterised by solution NMR spectroscopy and rationalises, in part, the formation of α,ß-unsaturated esters under catalytic conditions, thus providing useful principles for optimised catalyst design.

High-performance and long-term stability of mesoporous Cu-doped TiO2 microsphere for catalytic CO oxidation.

Although the low-temperature reaction mechanism of catalytic CO oxidation reaction remains unclear, the active sites of copper play a crucial role in this mechanism. One-step aerosol-assisted self-assembly (AASA) process has been developed for the synthesis of mesoporous Cu-doped TiO2 microspheres (CuTMS) to incorporate copper into the TiO2 lattice. This strategy highly enhanced the dispersion of copper from 41.10 to 83.65%. Long-term stability of the as-synthesized CuTMS materials for catalytic CO oxidation reaction was monitored using real-time mass spectrum. Isolated CuO and Cu-O-Ti were formed as determined by X-ray photoelectron spectroscopy (XPS). The formation of the Cu-O-Ti bonds in the crystal lattice changes the electron densities of Ti(IV) and O, causing a subsequent change in Ti(III)/Ti(IV) and Onon/OTotal ratio. 20CuTMS contained the highest lattice distortion (0.44) in which the Onon/OTotal ratio is lowest (0.18). This finding may be attributed to the absolute formation of the Cu-O-Ti bonds in the crystal lattice. However, the decrease of Ti(III)/Ti(IV) ratio to about 0.35 of 25CuTMS was caused by the CuO cluster formation on the surface. N2O titration-assisted H2 temperature-programmed reduction and in-situ Fourier transform infrared spectroscopy revealed the properties of copper and effects of active sites.

Epitaxial and Strong Support Interactions between Pt and LaFeO3 Films Stabilize Pt Dispersion.

The ability to stabilize very small Pt crystallites in supported-metal catalysts following harsh treatments is an important industrial problem. Here, we demonstrate that Pt particles can be maintained in the 1- to 2-nm range following multiple oxidation and reduction cycles at 1073 K when the particles are supported on 0.5-nm LaFeO3 films that have been deposited onto MgAl2O4 using atomic layer deposition. Characterization by scanning transmission electron microscopy suggests that when the catalyst is oxidized at 1073 K, the Pt crystallites are oriented with respect to the underlying LaFeO3. X-ray absorption spectroscopy also shows evidence of changes in the Pt environment. CO-oxidation rates for the reduced catalyst remain unchanged after five redox cycles at 1073 K. Epitaxial growth of Pt clusters and the consequent strong metal-support interaction between Pt and LaFeO3 are suggested to be the main reasons for the enhanced catalytic performances.

Solar Thermoplasmonic Nanofurnace for High-Temperature Heterogeneous Catalysis.

Most of existing solar thermal technologies require highly concentrated solar power to operate in the temperature range 300-600 °C. Here, thin films of refractory plasmonic TiN cylindrical nanocavities manufactured via flexible and scalable process are presented. The fabricated TiN films show polarization-insensitive 95% broadband absorption in the visible and near-infrared spectral ranges and act as plasmonic "nanofurnaces" capable of reaching temperatures above 600 °C under moderately concentrated solar irradiation (∼20 Suns). The demonstrated structures can be used to control nanometer-scale chemistry with zeptoliter (10-21 L) volumetric precision, catalyzing C-C bond formation and melting inorganic deposits. Also shown is the possibility to perform solar thermal CO oxidation at rates of 16 mol h-1 m-2 and with a solar-to-heat thermoplasmonic efficiency of 63%. Access to scalable, cost-effective refractory plasmonic nanofurnaces opens the way to the development of modular solar thermal devices for sustainable catalytic processes.

Cerium Oxide Nanoparticles Absorption through Intact and Damaged Human Skin.

Cerium oxide (CeO2) nanoparticles (NPs) are used in polishing products and absorbents, as promoters in wound healing, and as organopesticide decontaminants. While systemic bioaccumulation and organ toxicity has been described after inhalation, data on CeO2 NPs' transdermal permeation are lacking. Our study was an in vitro investigation of the permeation of 17-nm CeO2 NPs dispersed in synthetic sweat (1 g L-1) using excised human skin on Franz cells. Experiments were performed using intact and needle-abraded skin, separately. The average amount of Ce into intact and damaged skin samples was 3.64 ± 0.15 and 7.07 ± 0.78 µg cm-2, respectively (mean ± SD, p = 0.04). Ce concentration in the receiving solution was 2.0 ± 0.4 and 3.3 ± 0.7 ng cm-2 after 24 h (p = 0.008). The Ce content was higher in dermal layers of damaged skin compared to intact skin (2.93 ± 0.71 µg cm-2 and 0.39 ± 0.16 µg cm-2, respectively; p = 0.004). Our data showed a very low dermal absorption and transdermal permeation of cerium, providing a first indication of Ce skin uptake due to contact with CeO2.

Cross-Linked Carbon Nanotube Adsorbents for Water Treatment: Tuning the Sorption Capacity through Chemical Functionalization.

The development of carbon-based membrane adsorbent materials for water treatment has become a hot topic in recent years. Among them, carbon nanotubes (CNTs) are promising materials because of its large surface area, high aspect ratio, great chemical reactivity, and low cost. In this work, free-standing CNT adsorbents are fabricated from chemically cross-linked single-walled CNTs. We have demonstrated that by controlling the degree of cross-linking, the nanostructure, porous features, and specific surface area of the resulting materials can be tuned, in turn allowing the control of the adsorption capacities and the improvement of the adsorption performance. The cross-linked CNT adsorbents exhibit a notably selective sorption ability and good recyclability for removal of organics and oils from contaminated water.

Mixed-Valence Single-Atom Catalyst Derived from Functionalized Graphene.

Single-atom catalysts (SACs) aim at bridging the gap between homogeneous and heterogeneous catalysis. The challenge is the development of materials with ligands enabling coordination of metal atoms in different valence states, and preventing leaching or nanoparticle formation. Graphene functionalized with nitrile groups (cyanographene) is herein employed for the robust coordination of Cu(II) ions, which are partially reduced to Cu(I) due to graphene-induced charge transfer. Inspired by nature's selection of Cu(I) in enzymes for oxygen activation, this 2D mixed-valence SAC performs flawlessly in two O2 -mediated reactions: the oxidative coupling of amines and the oxidation of benzylic CH bonds toward high-value pharmaceutical synthons. High conversions (up to 98%), selectivities (up to 99%), and recyclability are attained with very low metal loadings in the reaction. The synergistic effect of Cu(II) and Cu(I) is the essential part in the reaction mechanism. The developed strategy opens the door to a broad portfolio of other SACs via their coordination to various functional groups of graphene, as demonstrated by successful entrapment of FeIII /FeII single atoms to carboxy-graphene.

SUNSPACE, A Porous Material to Reduce Air Particulate Matter (PM).

The World Health Organization reports that every year several million people die prematurely due to air pollution. Poor air quality is a by-product of unsustainable policies in transportation, energy, industry, and waste management in the world's most crowded cities. Particulate matter (PM) is one of the major element of polluted air. PM can be composed by organic and inorganic species. In particular, heavy metals present in PM include, lead (Pb), mercury (Hg), cadmium, (Cd), zinc (Zn), nickel (Ni), arsenic (As), and molybdenum (Mo). Currently, vegetation is the only existing sustainable method to reduce anthropogenic PM concentrations in urban environments. In particular, the PM-retention ability of vegetation depends on the surface properties, related to the plant species, leaf and branch density, and leaf micromorphology. In this work, a new hybrid material called SUNSPACE (SUstaiNable materials Synthesized from by-Products and Alginates for Clean air and better Environment) is proposed for air PM entrapment. Candle burning tests are performed to compare SUNSPACE with Hedera Helix L. leafs with respect to their efficacy of reducing coarse and fine PM. The temporal variation of PM10 and PM2.5 in presence of the trapping materials, shows that Hedera Helix L. surface saturates more rapidly. In addition, the capability of SUNSPACE in ultrafine PM trapping is also demonstrated by using titanium dioxide nanoparticles with 25 nm diameter. Scanning electron microscope (SEM) and Transmission electron microscope (TEM) images of SUNSPACE after entrapment tests highlight the presence of collected nanoparticles until to about 0.04 mm in depth from the sample surface. N2 physisorption measurements allow to demonstrate the possibility to SUNSPACE regeneration by washing.

A New Porous Hybrid Material Derived From Silica Fume and Alginate for Sustainable Pollutants Reduction.

In this work a new mesoporous adsorbent material obtained from a natural, high abundant raw material and a high volume industrial by-product is presented. The material is consolidated by the gelling properties of alginate and by decomposition of sodium-bicarbonate controlled porosity at low temperatures (70-80°C) at different scale lengths. The structural, thermal, and morphological characterization shows that the material is a mesoporous organic-inorganic hybrid. The material is tested as adsorbent, showing high performances. Methylene blue, used as model pollutant, can be adsorbed and removed from aqueous solutions even at a high concentration with efficiency up to 94%. By coating the material with a 100 nm thin film of titania, good photodegradation performance (more than 20%) can be imparted. Based on embodied energy and carbon footprint of its primary production, the sustainability of the new obtained material is evaluated and quantified in respect to activated carbon as well. It is shown that the new proposed material has an embodied energy lower than one order of magnitude in respect to the one of activated carbon, which represents the gold standards. The versatility of the new material is also demonstrated in terms of its design and manufacturing possibilities In addition, this material can be printed in 3D. Finally, preliminary results about its ability to capture diesel exhaust particulate matter are reported. The sample exposed to diesel contains a large amount of carbon in its surface. At the best of our knowledge, this is the first time that hybrid porous materials are proposed as a new class of sustainable materials, produced to reduce pollutants in the wastewaters and in the atmosphere.

Smart Pd Catalyst with Improved Thermal Stability Supported on High-Surface-Area LaFeO3 Prepared by Atomic Layer Deposition.

The concept of self-regenerating or "smart" catalysts, developed to mitigate the problem of supported metal particle coarsening in high-temperature applications, involves redispersing large metal particles by incorporating them into a perovskite-structured support under oxidizing conditions and then exsolving them as small metal particles under reducing conditions. Unfortunately, the redispersion process does not appear to work in practice because the surface areas of the perovskite supports are too low and the diffusion lengths for the metal ions within the bulk perovskite too short. Here, we demonstrate reversible activation upon redox cycling for CH4 oxidation and CO oxidation on Pd supported on high-surface-area LaFeO3, prepared as a thin conformal coating on a porous MgAl2O4 support using atomic layer deposition. The LaFeO3 film, less than 1.5 nm thick, was shown to be initially stable to at least 900 °C. The activated catalysts exhibit stable catalytic performance for methane oxidation after high-temperature treatment.

Towards Sustainable H2 Production: Rational Design of Hydrophobic Triphenylamine-based Dyes for Sensitized Ethanol Photoreforming.

Donor-acceptor dyes are a well-established class of photosensitizers, used to enhance visible-light harvesting in solar cells and in direct photocatalytic reactions, such as H2 production by photoreforming of sacrificial electron donors (SEDs). Amines-typically triethanolamine (TEOA)-are commonly employed as SEDs in such reactions. Dye-sensitized photoreforming of more sustainable, biomass-derived alcohols, on the other hand, was only recently reported by using methanol as the electron donor. In this work, several rationally designed donor-acceptor dyes were used as sensitizers in H2 photocatalytic production, comparing the efficiency of TEOA and EtOH as SEDs. In particular, the effect of hydrophobic chains in the spacer and/or the donor unit of the dyes was systematically studied. The H2 production rates were higher when TEOA was used as SED, whereas the activity trends depended on the SED used. The best performance was obtained with TEOA by using a sensitizer with just one bulky hydrophobic moiety, propylenedioxythiophene, placed on the spacer unit. In the case of EtOH, the best-performing sensitizers were the ones featuring a thiazolo[5,4-d]thiazole internal unit, needed for enhancing light harvesting, and carrying alkyl chains on both the donor part and the spacer unit. The results are discussed in terms of reaction mechanism, interaction with the SED, and structural/electrochemical properties of the sensitizers.

Palladium nanoparticles exposure: Evaluation of permeation through damaged and intact human skin.

The intensified use of palladium nanoparticles (PdNPs) in many chemical reactions, jewellery, electronic devices, in car catalytic converters and in biomedical applications lead to a significant increase in palladium exposure. Pd can cause allergic contact dermatitis when in contact with the skin. However, there is still a lack of toxicological data related to nano-structured palladium and information on human cutaneous absorption. In fact, PdNPs, can be absorbed through the skin in higher amounts than bulk Pd because NPs can release more ions. In our study, we evaluated the absorption of PdNPs, with a size of 10.7 ± 2.8 nm, using intact and damaged human skin in Franz cells. 0.60 mg cm(-2) of PdNPs were applied on skin surface for 24 h. Pd concentrations in the receiving solutions at the end of experiments were 0.098 ± 0.067 µg cm(-2) and 1.06 ± 0.44 µg cm(-2) in intact skin and damaged skin, respectively. Pd flux permeation after 24 h was 0.005 ± 0.003 µg cm(-2) h(-1) and 0.057 ± 0.030 µg cm(-2) h(-1) and lag time 4.8 ± 1.7 and 4.2 ± 3.6 h, for intact and damaged skin respectively. This study indicates that Pd can penetrate human skin.

Engineering titania nanostructure to tune and improve its photocatalytic activity.

Photocatalytic pathways could prove crucial to the sustainable production of fuels and chemicals required for a carbon-neutral society. Electron-hole recombination is a critical problem that has, so far, limited the efficiency of the most promising photocatalytic materials. Here, we show the efficacy of anisotropy in improving charge separation and thereby boosting the activity of a titania (TiO2) photocatalytic system. Specifically, we show that H2 production in uniform, one-dimensional brookite titania nanorods is highly enhanced by engineering their length. By using complimentary characterization techniques to separately probe excited electrons and holes, we link the high observed reaction rates to the anisotropic structure, which favors efficient carrier utilization. Quantum yield values for hydrogen production from ethanol, glycerol, and glucose as high as 65%, 35%, and 6%, respectively, demonstrate the promise and generality of this approach for improving the photoactivity of semiconducting nanostructures for a wide range of reacting systems.

Fundamentals and Catalytic Applications of CeO2-Based Materials.

Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40(th) anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are deepening our understanding of these materials, helping us to predict their behavior and application potential. This review has a wide view on all those aspects related to ceria which promise to produce an important impact on our life, encompassing fundamental knowledge of CeO2 and its properties, characterization toolbox, emerging features, theoretical studies, and all the catalytic applications, organized by their degree of establishment on the market.

Tuning Thiophene-Based Phenothiazines for Stable Photocatalytic Hydrogen Production.

Dibranched donor-(π-acceptor)2 dyes, where phenothiazine is the donor core, cyanoacrylic acid is the acceptor/anchoring group, and π is represented by mono- and poly-cyclic simple and fused thiophene derivatives, were tested as photosensitizers in the photocatalytic production of H2 , in combination with a Pt/TiO2 catalyst. The optical and electrochemical properties of the dyes were investigated, showing that careful design of the thiophene-based π spacer afforded enhanced optical properties. In the H2 production over 20 h, the new thiophene-based sensitizers revealed improved stability after longer irradiation times and enhanced performances, in terms of H2 production rates and light-to-fuel efficiencies, after an initial activation period, which were for the first time associated with enhanced stability under photocatalytic production of H2 and the absence of critical dye degradation.