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.

An oscillating reaction to produce clean fuels.

Understanding chemical reaction mechanisms could help synthesize sustainable fuels.

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.

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.

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.

Copper Cocatalyst Modulated Radical Generation for Selective Heterogeneous Photosynthesis of α-Haloketones.

The α-haloketones are important precursors for synthetic chemistry and pharmaceutical applications; however, their production relies heavily on traditional synthetic methods via halogenation of ketones that are toxic and environmentally risky. Here, we report a heterogeneous photosynthetic strategy of α-haloketone production from aromatic olefins using copper-modified graphitic carbon nitride (Cu-C3N4) under mild reaction conditions. By employing NiX2 (X = Cl, Br) as the halogen source, a series of α-haloketones can be synthesized using atmospheric air as the oxidant under visible-light irradiation. In comparison with pristine carbon nitride, the addition of Cu as a cocatalyst provides a moderate generation rate of halogen radicals and selective reduction of molecular oxygen into •OOH radicals, thus leading to a high selectivity to α-haloketones. The Cu-C3N4 also exhibits high stability and versatility, rendering it a promising candidate for solar-driven synthetic applications.

Copper dendrite stabilized NiFe(OH)x electrocatalyst for durable alkaline hydrogen evolution over 1000 h.

Durable Cu/NiFe(OH)x electrocatalyst was designed for hydrogen evolution reaction in alkaline media. The in situ generated Cu nanodendrites protect the NiFe(OH)x from being hydrogenated, giving it a > 1000 h lifetime for high-performance water splitting (1.51 V, 10 mA cm-2 in 1 M KOH) when coupled with a NiFe-layered double hydroxide anode.

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.

Boosting Photocatalytic Hydrogen Production by Modulating Recombination Modes and Proton Adsorption Energy.

Solar-driven production of renewable energy (e.g., H2) has been investigated for decades. To date, the applications are limited by low efficiency due to rapid charge recombination (both radiative and nonradiative modes) and slow reaction rates. Tremendous efforts have been focused on reducing the radiative recombination and enhancing the interfacial charge transfer by engineering the geometric and electronic structure of the photocatalysts. However, fine-tuning of nonradiative recombination processes and optimization of target reaction paths still lack effective control. Here we show that minimizing the nonradiative relaxation and the adsorption energy of photogenerated surface-adsorbed hydrogen atoms are essential to achieve a longer lifetime of the charge carriers and a faster reaction rate, respectively. Such control results in a 16-fold enhancement in photocatalytic H2 evolution and a 15-fold increase in photocurrent of the crystalline g-C3N4 compared to that of the amorphous g-C3N4.

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.

Light-tuned selective photosynthesis of azo- and azoxy-aromatics using graphitic C3N4.

Solar-driven photocatalysis has attracted significant attention in water splitting, CO2 reduction and organic synthesis. The syntheses of valuable azo- and azoxyaromatic dyes via selective photoreduction of nitroaromatic compounds have been realised using supported plasmonic metal nanoparticles at elevated temperatures (≥90 °C); however, the high cost, low efficiency and poor selectivity of such catalyst systems at room temperature limit their application. Here we demonstrate that the inexpensive graphitic C3N4 is an efficient photocatalyst for selective syntheses of a series of azo- and azoxy-aromatic compounds from their corresponding nitroaromatics under either purple (410 nm) or blue light (450 nm) excitation. The high efficiency and high selectivity towards azo- and azoxy-aromatic compounds can be attributed to the weakly bound photogenerated surface adsorbed H-atoms and a favourable N-N coupling reaction. The results reveal financial and environmental potential of photocatalysis for mass production of valuable chemicals.

First-principles elucidation of the surface chemistry of the C(2)H(x) (x = 0-6) adsorbate series on Fe(100).

Ab initio total-energy calculations of the elementary reaction steps leading to acetylene, ethylene and ethane formation and their decomposition on Fe(100) are described. Alongside the endothermicity of all the formation reactions, the crucial role played by adsorbed ethyl as main precursor towards both ethylene and ethane formation, characterises Fe(100) surface reactivity towards C(2)H(x) (x = 0-6) hydrocarbon formation in the low coverage limit. A comprehensive scheme based on three viable mechanisms towards ethyl formation on Fe(100), including methyl/methylene coupling, methyl/methylidyne coupling followed by one hydrogenation and methyl/carbon coupling followed by two hydrogenations, is the main result of this article.

Interactions between co-adsorbed CO and H on a Rh(100) single crystal surface.

Co-adsorption of CO and H(2) on a Rh(100) single crystal surface has been studied by a combination of temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), low energy electron diffraction (LEED), and density functional theory (DFT) calculations. Exposure of CO to a hydrogen precovered surfaces at 150 K results in some displacement of adsorbed hydrogen and a layer with 0.67 ML H and 0.67 ML CO is obtained. A c(3 square root(2) x square root(2))R45 degree structure is formed with CO occupying bridge sites and hydrogen occupying partly bridge sites on the surface and partly octahedral subsurface sites, causing hydrogen to desorb at temperatures around 230 K.

Chemistry of ethylene glycol on a Rh(100) single-crystal surface.

The adsorption and decomposition of ethylene glycol on Rh(100) have been studied with temperature-programmed reaction spectroscopy and reflection absorption infrared spectroscopy. Ethylene glycol adsorbs onto the surface via the hydroxyl groups. At 150 K, both hydroxyl bonds are broken, forming an ethylenedioxy intermediate. At high coverage, a portion of the ethylene glycol molecules dehydrogenate only one hydroxyl bond, forming a monodentate species. These intermediates decompose further, with complete dehydrogenation and simultaneous C--C bond breaking occurring at around 290 K. Hydrogen and carbon monoxide are formed, which desorb at 290 and 500 K, respectively.

Direct catalytic route to superhydrophobic polyethylene films.

Polyethylene films grow on a flat silica surface modified by the bis(imino)pyridyl iron(II) catalyst during ethylene polymerization in toluene solvent. The resulting films show superhydrophobic properties. Advancing water contact angle as high as 169 degrees and sliding angles as low as 2 degrees are obtained on these films. SEM images reveal special surface structures of these films containing micrometer-sized islands, submicrometer particles on the islands, and stress nanofibers between the islands, which render superhydrophobicity to the polyethylene surfaces. After the submicrometer particles and stress nanofibers are removed by annealing, the superhydrophobic properties of the polymer films disappear.

Acetylene decomposition on Rh(100): theory and experiment.

The decomposition of acetylene on a Rh(100) single crystal was studied by a combination of experimental techniques [static secondary ion mass spectrometry (SSIMS), temperature-programmed desorption (TPD), and low-energy electron diffraction (LEED)] to gain insight into the reaction pathway and the nature of the reaction intermediates. The experimental techniques were combined with a computational approach using density functional theory (DFT). Acetylene adsorbs irreversibly on the Rh(100) surface and eventually decomposes to atomic carbon and gas-phase hydrogen. The combination of experimental and computational results enabled us to determine the most likely reaction pathway for the decomposition process.