Creating and Stabilizing an Oxidized Pd Surface under Reductive Conditions for Photocatalytic Hydrogenation of Aromatic Carbonyls.

Photocatalysis provides an eco-friendly route for the hydrogenation of aromatic carbonyls to O-free aromatics, which is an important refining process in the chemical industry that is generally carried out under high pressure of hydrogen at elevated temperatures. However, aromatic carbonyls are often only partially hydrogenated to alcohols, which readily desorbs and are hardly further deoxygenated under ambient conditions. Here, we show that by constructing an oxide surface over the Pd cocatalyst supported on graphitic carbon nitride, an alternative hydrogenation path of aromatic carbonyls becomes available via a step-wise acetalization and hydrogenation, thus allowing efficient and selective production of O-free aromatics. The PdO surface allows for optimum adsorption of reactants and intermediates and rapid abstraction of hydrogen from the alcohol donor, favoring fast acetalization of the carbonyls and their consecutive hydrogenation to O-free hydrocarbons. The photocatalytic hydrogenation of benzaldehyde into toluene shows a high selectivity of >90% and a quantum efficiency of ∼10.2% under 410 nm irradiation. By adding trace amounts of HCl to the reaction solution, the PdO surface remains stable and active for long-term operation at high concentrations, offering perspective for practical applications.

A Modular Tubular Flow System with Replaceable Photocatalyst Membranes for Scalable Coupling and Hydrogenation.

Heterogeneous photocatalysis is effective for the selective synthesis of value-added chemicals at lab-scale, yet falls short of requirements for mass production (low cost and user friendliness). Here we report the design and fabrication of a modular tubular flow system embedded with replaceable photocatalyst membranes for scalable photocatalytic C-C, C-N homocoupling and hydrogenation reactions, which can be operated in either circular and continuous flow mode with high performance. The photocatalyst membranes almost fully occupy the volume of the reactor, thus enabling optimal absorption of the incident light. Additionally, the porous structured photocatalyst membranes facilitate the mass transfer of the reactants to efficiently use the active sites, resulting in 0th -order reaction kinetics and a high space-time yield compared to the batch reaction system at practical application levels and prolonged reaction times.

Electric Field Enhanced Ammoxidation of Aldehydes Using Supported Fe Clusters Under Ambient Oxygen Pressure.

Heterogeneous catalytic ammoxidation provides an eco-friendly route for the cyanide-free synthesis of nitrile compounds, which are important precursors for synthetic chemistry and pharmaceutical applications. However, in general such a process requires high pressures of molecular oxygen at elevated temperatures to accelerate the oxygen reduction and imine dehydrogenation steps, which is highly risky in practical applications. Here, we report an electric field enhanced ammoxidation system using a supported Fe clusters catalyst (Fe/NC), which enables efficient synthesis of nitriles from the corresponding aldehydes under ambient air pressure at room temperature (RT). A synergistic effect between the external electric field and the Fe/NC catalyst promotes the ammonia activation and the dehydrogenation of the generated imine intermediates and avoids the unwanted backwards reaction to aldehydes. This electric field enhanced ammoxidation system presents high efficiency and selectivity for the conversion of a series of aldehydes under mild conditions with high durability, rendering it an attractive process for the green synthesis of nitriles with fragile functional groups.

Heterogeneous Photocatalytic Recycling of FeX2 /FeX3 for Efficient Halogenation of C-H Bonds Using NaX.

Environmental-friendly halogenation of C-H bonds using abundant, non-toxic halogen salts is in high demand in various chemical industries, yet the efficiency and selectivity of laboratory available protocols are far behind the conventional photolytic halogenation process which uses hazardous halogen sources. Here we report an FeX2 (X=Br, Cl) coupled semiconductor system for efficient, selective, and continuous photocatalytic halogenation using NaX as halogen source under mild conditions. Herein, FeX2 catalyzes the reduction of molecular oxygen and the consumption of generated oxygen radicals, thus boosting the generation of halogen radicals and elemental halogen for direct halogenation and indirect halogenation via the formation of FeX3 . Recycling of FeX2 and FeX3 during the photocatalytic process enables the halogenation of a wide range of hydrocarbons in a continuous flow, rendering it a promising method for applications.

Super-Robust Xanthine-Sodium Complexes on Au(111).

A widely accepted theory is that life originated from the hydrothermal environment in the primordial ocean. Nevertheless, the low desorption temperature from inorganic substrates and the fragileness of hydrogen-bonded nucleobases do not support the required thermal stability in such an environment. Herein, we report the super-robust complexes of xanthine, one of the precursors for the primitive nucleic acids, with Na. We demonstrate that the well-defined xanthine-Na complexes can only form when the temperature is ≥430 K, and the complexes keep adsorbed even at ≈720 K, presenting as the most thermally stable organic polymer ever reported on Au(111). This work not only justifies the necessity of high-temperature, Na-rich environment for the prebiotic biosynthesis but also reveals the robustness of the xanthine-Na complexes upon the harsh environment. Moreover, the complexes can induce significant electron transfer with the metal as inert as Au and hence lift the Au atoms up.

Photocatalytic Abstraction of Hydrogen Atoms from Water Using Hydroxylated Graphitic Carbon Nitride for Hydrogenative Coupling Reactions.

Employing pure water, the ultimate green source of hydrogen donor to initiate chemical reactions that involve a hydrogen atom transfer (HAT) step is fascinating but challenging due to its large H-O bond dissociation energy (BDEH-O =5.1 eV). Many approaches have been explored to stimulate water for hydrogenative reactions, but the efficiency and productivity still require significant enhancement. Here, we show that the surface hydroxylated graphitic carbon nitride (gCN-OH) only requires 2.25 eV to activate H-O bonds in water, enabling abstraction of hydrogen atoms via dehydrogenation of pure water into hydrogen peroxide under visible light irradiation. The gCN-OH presents a stable catalytic performance for hydrogenative N-N coupling, pinacol-type coupling and dehalogenative C-C coupling, all with high yield and efficiency, even under solar radiation, featuring extensive impacts in using renewable energy for a cleaner process in dye, electronic, and pharmaceutical industries.

In vitro single-cell dissection revealing the interior structure of cable bacteria.

Filamentous Desulfobulbaceae bacteria were recently discovered as long-range transporters of electrons from sulfide to oxygen in marine sediments. The long-range electron transfer through these cable bacteria has created considerable interests, but it has also raised many questions, such as what structural basis will be required to enable micrometer-sized cells to build into centimeter-long continuous filaments? Here we dissected cable bacteria cells in vitro by atomic force microscopy and further explored the interior, which is normally hidden behind the outer membrane. Using nanoscale topographical and mechanical maps, different types of bacterial cell-cell junctions and strings along the cable length were identified. More important, these strings were found to be continuous along the bacterial cells passing through the cell-cell junctions. This indicates that the strings serve an important function in maintaining integrity of individual cable bacteria cells as a united filament. Furthermore, ridges in the outer membrane are found to envelop the individual strings at cell-cell junctions, and they are proposed to strengthen the junctions. Finally, we propose a model for the division and growth of the cable bacteria, which illustrate the possible structural requirements for the formation of centimeter-length filaments in the recently discovered cable bacteria.

Subsurface-Carbon-Induced Local Charge of Copper for an On-Surface Displacement Reaction.

Transition-metal carbides have sparked unprecedented enthusiasm as high-performance catalysts in recent years. Still, the catalytic properties of copper carbide remain unexplored. By introducing subsurface carbon to Cu(111), a displacement reaction of a proton in a carboxyl acid group with a single Cu atom is demonstrated at the atomic scale and room temperature. Its occurrence is attributed to the C-doping-induced local charge of surface Cu atoms (up to +0.30 e/atom), which accelerates the rate of on-surface deprotonation via reduction of the corresponding energy barrier, thus enabling the instant displacement of a proton with a Cu atom when the molecules adsorb on the surface. This well-defined and robust Cuδ+ surface based on subsurface-carbon doping offers a novel catalytic platform for on-surface synthesis.

Graphene-Like Covalent Organic Framework with a Wide Band Gap Synthesized On Surface via Stepwise Reactions.

Developing graphene-like two-dimensional materials naturally possessing a band gap has sparked enormous interest. Thanks to the inherent wide band gap and high mobility in the 2D plane, covalent organic frameworks containing triazine rings (t-COFs) hold great promise in this regard, whilst the synthesis of single-layer t-COFs remains highly challenging. Herein, we present the fabrication of a well-defined graphene-like t-COF on Au(111). Instead of single/multiple-step single-type reactions commonly applied for on-surface synthesis, distinct stepwise on-surface reactions, including alkynyl cyclotrimerization, C-O bond cleavage, and C-H bond activation, are triggered on demand, leading to product evolution in a controlled step-by-step manner. Aside from the precise control in sophisticated on-surface synthesis, this work proposes a single-atomic-layer organic semiconductor with a wide band gap of 3.41 eV.

Dual-Stimuli Responsive Bismuth Nanoraspberries for Multimodal Imaging and Combined Cancer Therapy.

Development of stimuli-responsive theranostics is of great importance for precise cancer diagnosis and treatment. Herein, bovine serum albumin (BSA) modified bismuth nanoraspberries (Bi-BSA NRs) are developed as cancer theranostic agents for multimodal imaging and chemo-photothermal combination therapy. The Bi-BSA NRs are synthesized in aqueous phase via a facile reduction method using Bi2O3 nanospheres as the sacrificial template. The morphology, biocompatibility, photothermal effect, drug loading/releasing abilities, chemotherapy effect, synergistic chemo-photothermal therapy efficacy, and multimodal imaging capacities of Bi-BSA NRs have been investigated. The results show that the NRs possess multiple unique features including (i) raspberry-like morphology with high specific surface area (∼52.24 m2·g-1) and large cavity (total pore volume ∼0.30 cm3·g-1), promising high drug loading capacity (∼69 wt %); (ii) dual-stimuli responsive drug release, triggered by acidic pH and NIR laser irradiation; (iii) infrared thermal (IRT), photoacoustic (PA) and X-ray computed tomography (CT) trimodality imaging with the CT contrast enhanced efficiency as high as ∼66.7 HU·mL·mg-1; (iv) 100% tumor elimination through the combination chemo-photothermal therapy. Our work highlights the great potentials of Bi-BSA NRs as a versatile theranostics for multimodal imaging and combination therapy.

Solid Base Bi24 O31 Br10 (OH)δ with Active Lattice Oxygen for the Efficient Photo-Oxidation of Primary Alcohols to Aldehydes.

The selective oxidation of primary alcohols to aldehydes by O2 instead of stoichiometric oxidants (for example, MnVII , CrVI , and OsIV ) is an important but challenging process. Most heterogeneous catalytic systems (thermal and photocatalysis) require noble metals or harsh reaction conditions. Here we show that the Bi24 O31 Br10 (OH)δ photocatalyst is very efficient in the selective oxidation of a series of aliphatic (carbon chain from C1 to C10 ) and aromatic alcohols to their corresponding aldehydes/ketones under visible-light irradiation in air at room temperature, which would be challenging for conventional thermal and light-driven processes. High quantum efficiencies (71 % and 55 % under 410 and 450 nm irradiation) are reached in a representative reaction, the oxidation of isopropanol. We propose that the outstanding performance of the Bi24 O31 Br10 (OH)δ photocatalyst is associated with basic surface sites and active lattice oxygen that boost the dehydrogenation step in the photo-oxidation of alcohols.

Xanthine Quartets on Au(111).

The quartet of xanthine (X), a purine base ubiquitously distributed in most human body tissues and fluids, has been for the first time fabricated and visualized, as the first alternative purine quartet besides the known guanine (G)-quartet. The X-quartet network is demonstrated to be the most stable phase on Au(111). Unlike guanine, the fabrication of the X-quartets is not dependent on the presence of metal atoms, which makes it the first metal-free purine quartet. The X-quartet holds great promise to potentially construct artificial new DNA quadruplexes for genetic regulation and antitumor therapy. Moreover, both the X-quartet itself and the quartet networks favor homochirality, suggesting homochiral xanthine oligomers and the networks may have been formed as the precursors of the pristine oligonucleotides on primitive Earth.

Efficient Solar-Driven Hydrogen Transfer by Bismuth-Based Photocatalyst with Engineered Basic Sites.

Photocatalytic organic conversions involving a hydrogen transfer (HT) step have attracted much attention, but the efficiency and selectivity under visible light irradiation still needs to be significantly enhanced. Here we have developed a noble metal-free, basic-site engineered bismuth oxybromide [Bi24O31Br10(OH)δ] that can accelerate the photocatalytic HT step in both reduction and oxidation reactions, i.e., nitrobenzene to azo/azoxybenzene, quinones to quinols, thiones to thiols, and alcohols to ketones under visible light irradiation and ambient conditions. Remarkably, quantum efficiencies of 42% and 32% for the nitrobenzene reduction can be reached under 410 and 450 nm irradiation, respectively. The Bi24O31Br10(OH)δ photocatalyst also exhibits excellent performance in up-scaling and stability under visible light and even solar irradiation, revealing economic potential for industrial applications.

Filamentous bacteria transport electrons over centimetre distances.

Oxygen consumption in marine sediments is often coupled to the oxidation of sulphide generated by degradation of organic matter in deeper, oxygen-free layers. Geochemical observations have shown that this coupling can be mediated by electric currents carried by unidentified electron transporters across centimetre-wide zones. Here we present evidence that the native conductors are long, filamentous bacteria. They abounded in sediment zones with electric currents and along their length they contained strings with distinct properties in accordance with a function as electron transporters. Living, electrical cables add a new dimension to the understanding of interactions in nature and may find use in technology development.

Metal borohydrides and derivatives - synthesis, structure and properties.

A wide variety of metal borohydrides, MBH4, have been discovered and characterized during the past decade, revealing an extremely rich chemistry including fascinating structural flexibility and a wide range of compositions and physical properties. Metal borohydrides receive increasing interest within the energy storage field due to their extremely high hydrogen density and possible uses in batteries as solid state ion conductors. Recently, new types of physical properties have been explored in lanthanide-bearing borohydrides related to solid state phosphors and magnetic refrigeration. Two major classes of metal borohydride derivatives have also been discovered: anion-substituted compounds where the complex borohydride anion, BH4-, is replaced by another anion, i.e. a halide or amide ion; and metal borohydrides modified with neutral molecules, such as NH3, NH3BH3, N2H4, etc. Here, we review new synthetic strategies along with structural, physical and chemical properties for metal borohydrides, revealing a number of new trends correlating composition, structure, bonding and thermal properties. These new trends provide general knowledge and may contribute to the design and discovery of new metal borohydrides with tailored properties towards the rational design of novel functional materials. This review also demonstrates that there is still room for discovering new combinations of light elements including boron and hydrogen, leading to complex hydrides with extreme flexibility in composition, structure and properties.

Formation of Hypoxanthine Tetrad by Reaction with Sodium Chloride: From Planar to Stereo.

By reacting with NaCl on Au(111), the formation of hypoxanthine (HX) tetrads is demonstrated at the atomic scale in real space. These results directly demonstrate that alternative purine tetrads can be formed in both planar and non-planar configuration, and that ionic bonding plays a crucial role for the formation and planar-to-stereo transformation of the tetrads, providing deeper insight for constructing artificial DNA/RNA quadruplexes. Moreover, both the tilted HXs and Na show strong charge transfer with the substrate in the non-planar phase. The insights gained by this work also open up new routes to tune the electrostatic nature of metal-organic interfaces and design stereo-nanostructures on surfaces.

Phase-Transition Induced Conversion into a Photothermal Material: Quasi-Metallic WO2.9 Nanorods for Solar Water Evaporation and Anticancer Photothermal Therapy.

Phase transition from WO3 to sub-stoichiometric WO2.9 by a facile method has varied the typical semiconductor to be quasi-metallic with a narrowed band gap and a shifted Femi energy to the conduction band, while maintaining a high crystallinity. The resultant WO2.9 nanorods possess a high total absorption capacity (ca. 90.6 %) over the whole solar spectrum as well as significant photothermal conversion capability, affording a conversion efficiency as high as around 86.9 % and a water evaporation efficiency of about 81 % upon solar light irradiation. Meanwhile, the promising potential of the nanorods for anticancer photothermal therapy have been also demonstrated, with a high photothermal conversion efficiency (ca. 44.9 %) upon single wavelength near-infrared irradiation and a high tumor inhibition rate (ca. 98.5 %). This study may have opened up a feasible route to produce high-performance photothermal materials from well-developed oxides.

Two-dimensional material confined water.

CONSPECTUS: The interface between water and other materials under ambient conditions is of fundamental importance due to its relevance in daily life and a broad range of scientific research. The structural and dynamic properties of water at an interface have been proven to be significantly difference than those of bulk water. However, the exact nature of these interfacial water adlayers at ambient conditions is still under debate. Recent scanning probe microscopy (SPM) experiments, where two-dimensional (2D) materials as ultrathin coatings are utilized to assist the visualization of interfacial water adlayers, have made remarkable progress on interfacial water and started to clarify some of these fundamental scientific questions. In this Account, we review the recently conducted research exploring the properties of confined water between 2D materials and various surfaces under ambient conditions. Initially, we review the earlier studies of water adsorbed on hydrophilic substrates under ambient conditions in the absence of 2D coating materials, which shows the direct microscopic results. Subsequently, we focus on the studies of water adlayer growth at both hydrophilic and hydrophobic substrates in the presence of 2D coating materials. Ice-like water adlayers confined between hydrophobic graphene and hydrophilic substrates can be directly observed in detail by SPM. It was found that the packing structure of the water adlayer was determined by the hydrophilic substrates, while the orientation of intercalation water domains was directed by the graphene coating. In contrast to hydrophilic substrates, liquid-like nanodroplets confined between hydrophobic graphene and hydrophobic substrates appear close to step edges and atomic-scale surface defects, indicating that atomic-scale surface defects play significant roles in determining the adsorption of water on hydrophobic substrates. In addition, we also review the phenomena of confined water between 2D hydrophilic MoS2 and the hydrophilic substrate. Finally, we further discuss researchers taking advantage of 2D graphene coatings to stabilize confined water nanodroplets to manipulate nanofluidics through applying an external force by using novel SPM techniques. Moreover, for future technology application purposes, the doping effect of confined water is also discussed. The use of 2D materials as ultrathin coatings to investigate the properties of confined water under ambient conditions is developing and recognized as a profound approach to gain fundamental knowledge of water. This ideal model system will provide new opportunities in various research fields.

Self-assembly of hydrogen-bonded supramolecular complexes of nucleic-acid-base and fatty-acid at the liquid-solid interface.

Self-assembly provides an effective approach for the fabrication of supramolecular complexes or heterojunction materials, which have unique properties and potential applications in many fields. In this study, the self-assembled structures of stearic acid (SA) and nucleic acid base, guanine (G), are formed at the liquid-solid interface. Two main configurations, namely SA-G-SA and SA-G-G-SA, are observed and the intermolecular recognition mechanism between G and SA is proposed from the hydrogen-bonding point of view.

Synthesis and decomposition of Li3Na(NH2)4 and investigations of Li-Na-N-H based systems for hydrogen storage.

Previous studies have shown modified thermodynamics of amide-hydride composites by cation substitution, while this work systematically investigates lithium-sodium-amide, Li-Na-N-H, based systems. Li3Na(NH2)4 has been synthesized by combined ball milling and annealing of 3LiNH2-NaNH2 with LiNa2(NH2)3 as a minor by-product. Li3+xNa1-x(NH2)4 releases NaNH2 and forms non-stoichiometric Li3+xNa1-x(NH2)4 before it melts at 234 °C, as observed by in situ powder X-ray diffraction. Above 234 °C, Li3+xNa1-x(NH2)4 releases a mixture of NH3, N2 and H2 while a bi-metallic lithium sodium imide is not observed during decomposition. Hydrogen storage performances have been investigated for the composites Li3Na(NH2)4-4LiH, LiNH2-NaH and NaNH2-LiH. Li3Na(NH2)4-4LiH converts into 4LiNH2-NaH-3LiH during mechanochemical treatment and releases 4.2 wt% of H2 in multiple steps between 25 and 340 °C as revealed by Sievert's measurements. All three investigated composites have a lower peak temperature for H2 release as compared to LiNH2-LiH, possibly owing to modified kinetics and thermodynamics, due to the formation of Li3Na(NH2)4 and LiNa2(NH2)3.