Optimal Oxophilicity at the Fe-Nx Interface Enhances the Generation of Singlet Oxygen for Efficient Fenton-Like Catalysis.

In the pursuit of efficient singlet oxygen generation in Fenton-like catalysis, the utilization of single-atom catalysts (SACs) emerges as a highly desired strategy. Here, a discovery is reported that the single-atom Fe coordinated with five N-atoms on N-doped porous carbon, denoted as Fe-N5/NC, outperform its counterparts, those coordinated with four (Fe-N4/NC) or six N-atoms (Fe-N6/NC), as well as state-of-the-art SACs comprising other transition metals. Thus, Fe-N5/NC exhibits exceptional efficacy in activating peroxymonosulfate for the degradation of organic pollutants. The coordination number of N-atoms can be readily adjusted by pyrolysis of pre-assembly structures consisting of Fe3+ and various isomers of phenylenediamine. Fe-N5/NC displayed outstanding tolerance to environmental disturbances and minimal iron leaching when incorporated into a membrane reactor. A mechanistic study reveals that the axial ligand N reduces the contribution of Fe-3d orbitals in LUMO and increases the LUMO energy of Fe-N5/NC. This, in turn, reduces the oxophilicity of the Fe center, promoting the reactivity of *OO intermediate-a pivotal step for yielding singlet oxygen and the rate-determining step. These findings unveil the significance of manipulating the oxophilicity of metal atoms in single-atom catalysis and highlight the potential to augment Fenton-like catalysis performance using Fe-SACs.

High-Efficiency Solar Transformation of Sugars via Heterogeneous Gallium(III) Catalyst.

Extremely limited research exploring the photocatalytic potential of main group metals, such as aluminum, gallium, and tin, has been undertaken due to their weak light harvesting properties. This study reports the efficient transformation of sugars to 5-hydroxymethylfurfural (HMF) with high yield employing an original heterogenous photocatalyst comprising a gallium(III) complex immobilized on an alumina support. Under visible light irradiation, the reaction rate of HMF formation is ~143 times higher than the equivalent thermal reaction performed in the absence of light. The turnover number (TON) the heterogeneous gallium (III) photocatalyst was as high as 1500, which was two orders of magnitude higher than the TON of the homogeneous gallium (III) system. It is proposed that photoirradiation significantly enhances the Lewis acidity of the catalyst by forming a semi-coordination state between gallium(III) and N-donor ligands, enabling the increased interaction of reactant sugar molecules with gallium(III) active sites. Consistent with this, the photoresponsive coordination of the gallium(III) complex and the abstraction of the hydroxy group by the metal under irradiation with visible light is observed by NMR spectroscopy for the first time. These findings demonstrate that efficient photocatalysts derived from the main group elements can facilitate biomass conversion using visible light.

Plasmonic Silver-Nanoparticle-Catalysed Hydrogen Abstraction from the C(sp3 )-H Bond of the Benzylic Cα atom for Cleavage of Alkyl Aryl Ether Bonds.

Selective activation of the C(sp3 )-H bond is an important process in organic synthesis, where efficiently activating a specific C(sp3 )-H bond without causing side reactions remains one of chemistry's great challenges. Here we report that illuminated plasmonic silver metal nanoparticles (NPs) can abstract hydrogen from the C(sp3 )-H bond of the Cα atom of an alkyl aryl ether ß-O-4 linkage. The intense electromagnetic near-field generated at the illuminated plasmonic NPs promotes chemisorption of the ß-O-4 compound and the transfer of photo-generated hot electrons from the NPs to the adsorbed molecules leads to hydrogen abstraction and direct cleavage of the unreactive ether Cß -O bond under moderate reaction conditions (≈90 °C). The plasmon-driven process has certain exceptional features: enabling hydrogen abstraction from a specific C(sp3 )-H bond, along with precise scission of the targeted C-O bond to form aromatic compounds containing unsaturated, substituted groups in excellent yields.

High Nitrile Yields of Aerobic Ammoxidation of Alcohols Achieved by Generating •O2- and Br• Radicals over Iron-Modified TiO2 Photocatalysts.

Catalytic ammoxidation of alcohols into nitriles is an essential reaction in organic synthesis. While highly desirable, conducting the synthesis at room temperature is challenging, using NH3 as the nitrogen source, O2 as the oxidant, and a catalyst without noble metals. Herein, we report robust photocatalysts consisting of Fe(III)-modified titanium dioxide (Fe/TiO2) for ammoxidation reactions at room temperature utilizing oxygen at atmospheric pressure, NH3 as the nitrogen source, and NH4Br as an additive. To the best of our knowledge, this is the first example of catalytic ammoxidation of alcohols over a photocatalyst using such cheap and benign materials. Various (hetero) aromatic nitriles were synthesized at high yields, and aliphatic alcohols could also be transformed into corresponding nitriles at considerable yields. The modification of TiO2 with Fe(III) facilitates the formation of active •O2- radicals and increases the adsorption of NH3 and amino intermediates on the catalyst, accelerating the ammoxidation to yield nitriles. The additive NH4Br impressively improves the catalytic efficiency via the formation of bromine radicals (Br•) from Br-, which works synergistically with •O2- to capture H• from Cα-H, which is present in benzyl alcohol and the intermediate aldimine (RCH═NH), to generate the active carbon-centered radicals. Further, the generation of Br• from the Br- additive consumes the photogenerated holes and OH• radicals to prevent over-oxidation, significantly improving the selectivity toward nitriles. This amalgamation of function and synergy of the Fe(III)-doped TiO2 and NH4Br reveals new opportunities for developing semiconductor-based photocatalytic systems for fine chemical synthesis.

Plasmonic Switching of the Reaction Pathway: Visible-Light Irradiation Varies the Reactant Concentration at the Solid-Solution Interface of a Gold-Cobalt Catalyst.

Product selectivity of alkyne hydroamination over catalytic Au2 Co alloy nanoparticles (NPs) can be made switchable by a light-on/light-off process, yielding imine (cross-coupling product of aniline and alkyne) under visible-light irradiation, but 1,4-diphenylbutadiyne in the dark. The low-flux light irradiation concentrates aniline on the catalyst, accelerating the catalytic cross-coupling by several orders of magnitude even at a very low overall aniline concentrations (1.0×10-3  mol L-1 ). A tentative mechanism is that Au2 Co NPs absorb light, generating an intense fringing electromagnetic field and hot electrons. The sharp field-gradient (plasmonic optical force) can selectively enhance adsorption of light-polarizable aniline molecules on the catalyst. The light irradiation thereby alters the aniline/alkyne ratio at the NPs surface, switching product selectivity. This represents a new paradigm to modify a catalysis process by light.

Copper nanoparticles on graphene support: an efficient photocatalyst for coupling of nitroaromatics in visible light.

Copper is a low-cost plasmonic metal. Efficient photocatalysts of copper nanoparticles on graphene support are successfully developed for controllably catalyzing the coupling reactions of aromatic nitro compounds to the corresponding azoxy or azo compounds under visible-light irradiation. The coupling of nitrobenzene produces azoxybenzene with a yield of 90 % at 60 °C, but azobenzene with a yield of 96 % at 90 °C. When irradiated with natural sunlight (mean light intensity of 0.044 W cm(-2) ) at about 35 °C, 70 % of the nitrobenzene is converted and 57 % of the product is azobenzene. The electrons of the copper nanoparticles gain the energy of the incident light through a localized surface plasmon resonance effect and photoexcitation of the bound electrons. The excited energetic electrons at the surface of the copper nanoparticles facilitate the cleavage of the NO bonds in the aromatic nitro compounds. Hence, the catalyzed coupling reaction can proceed under light irradiation and moderate conditions. This study provides a green photocatalytic route for the production of azo compounds and highlights a potential application for graphene.

Viable photocatalysts under solar-spectrum irradiation: nonplasmonic metal nanoparticles.

Supported nanoparticles (NPs) of nonplasmonic transition metals (Pd, Pt, Rh, and Ir) are widely used as thermally activated catalysts for the synthesis of important organic compounds, but little is known about their photocatalytic capabilities. We discovered that irradiation with light can significantly enhance the intrinsic catalytic performance of these metal NPs at ambient temperatures for several types of reactions. These metal NPs strongly absorb the light mainly through interband electronic transitions. The excited electrons interact with the reactant molecules on the particles to accelerate these reactions. The rate of the catalyzed reaction depends on the concentration and energy of the excited electrons, which can be increased by increasing the light intensity or by reducing the irradiation wavelength. The metal NPs can also effectively couple thermal and light energy sources to more efficiently drive chemical transformations.

Photocatalytic conversion of sugars to 5-hydroxymethylfurfural using aluminium(III) and fulvic acid.

5-hydroxymethylfurfural (HMF) is a valuable and essential platform chemical for establishing a sustainable, eco-friendly fine-chemical and pharmaceutical industry based on biomass. The cost-effective production of HMF from abundant C6 sugars requires mild reaction temperatures and efficient catalysts from naturally abundant materials. Herein, we report how fulvic acid forms complexes with Al3+ ions that exhibit solar absorption and photocatalytic activity for glucose conversion to HMF in one-pot reaction, in good yield (~60%) and at moderate temperatures (80 °C). When using representative components of fulvic acid, catechol and pyrogallol as ligands, 70 and 67% HMF yields are achieved, respectively, at 70 °C. Al3+ ions are not recognised as effective photocatalysts; however, complexing them with fulvic acid components as light antennas can create new functionality. This mechanism offers prospects for new green photocatalytic systems to synthesise a range of substances that have not previously been considered.

Nanostructure Shape-Effects in ZnO heterogeneous photocatalysis.

Selective oxidation of alcohols is an essential reaction for fine chemical production. Here, the photocatalytic oxidation of benzyl alcohol by zinc oxide (ZnO) nanocrystals was investigated to clarify the mechanism of selective oxidation with this process. Reactivity when in contact with three distinct ZnO nanocrystal shapes: nanocones, nanorods and nanoplates, was studied in order to compare crystal facet-specific effects in the reaction system. The same non-hydrothermal and non-hydrolytic aminolysis method was used to synthesise all three nanocrystal shapes. The ZnO catalysts were characterized using by a range of techniques to establish the key properties of the prominent ZnO crystal facets exposed to the reaction medium. The ZnO nanocrystals photocatalysed the benzyl alcohol oxidation reaction when irradiated by a 370 - 375 nm LED output and each ZnO crystal morphology exhibited different reaction kinetics for the oxidation reaction. ZnO nanocones displayed the highest benzyl alcohol conversion rate while nanorods gave the lowest. This established a facet-dependent kinetic activity for the benzyl alcohol reaction of (101¯1) > (0001) > (101¯0). Experimental and density functional theory computation results confirm that the {101¯1} facet is a surface that exposes undercoordinated O atoms to the reaction medium, which explains why the reactant benzyl alcohol adsorption on this facet is the highest. Light irradiation can excite valence band electrons to the conduction band, which are then captured by O2 molecules to yield superoxide (O2•-). In a non-aqueous solvent, the photogenerated holes oxidise benzyl alcohol to form a radical species, which reacts with O2•- to yield benzaldehyde. This results in 100% product selectivity for benzaldehyde, rather than the carboxylic acid derivative.

Oxidative Esterification of 5-Hydroxymethylfurfural into Dimethyl 2,5-Furandicarboxylate Using Gamma Alumina-Supported Gold Nanoparticles.

Gold nanoparticles (Au NPs) supported on a nanostructured gamma alumina (γ-Al2O3) fiber can exhibit excellent catalytic activity for the conversion of 5-hydroxymethylfurfural to produce its ester derivative, dimethyl 2,5-furandicarboxylate (FDMC). γ-Al2O3 was synthesized using a PEG surfactant to generate oxide fibers that randomly stack together into irregular shapes. The average particle sizes of the Au NPs are 1-6 nm, where the catalytically active Au (111) surface is the exposed facet. This 3D nanocatalyst architecture enhances the 5-hydroxymethylfurfural (HMF) oxidative esterification because HMF reactant molecules can readily diffuse into this fibrous structure and adsorb to active catalytic sites, while ester product molecules can diffuse out. Up to 99% HMF conversion and 90% FDMC selectivity can be obtained at a low reaction temperature of 45 °C, and the catalyst shows excellent recyclability. Increasing the Au content in the catalyst minimizes the requirement of a base for HMF conversion. Thus, the Au NPs supported on γ-Al2O3 can drive HMF esterification to FDMC efficiently with high product selectivity under very mild reaction conditions, omitting the need for an additional esterification step of the HMF acid.

Ceramic membranes for separation of proteins and DNA through in situ growth of alumina nanofibres inside porous substrates.

Ceramic membranes were fabricated by in situ synthesis of alumina nanofibres in the pores of an alumina support as a separation layer, and exhibited a high permeation selectivity for bovine serum albumin relative to bovine hemoglobin (over 60 times) and can effectively retain DNA molecules at high fluxes.

Titanate nanofibers as intelligent absorbents for the removal of radioactive ions from water.

Layered titanate nanofibers can absorb bivalent ions from waste water via an ion exchange process. The sorption induces a considerable deformation of the layered structure, thus trapping the cations in the fibers permanently. Therefore, the fibers are desirable sorbents for the removal of toxic, radioactive Ra(2+) and Sr(2+) ions from water and subsequent safe disposal thereof.

High-flux ceramic membranes with a nanomesh of metal oxide nanofibers.

Traditional ceramic separation membranes, which are fabricated by applying colloidal suspensions of metal hydroxides to porous supports, tend to suffer from pinholes and cracks that seriously affect their quality. Other intrinsic problems for these membranes include dramatic losses of flux when the pore sizes are reduced to enhance selectivity and dead-end pores that make no contribution to filtration. In this work, we propose a new strategy for addressing these problems by constructing a hierarchically structured separation layer on a porous substrate using large titanate nanofibers and smaller boehmite nanofibers. The nanofibers are able to divide large voids into smaller ones without forming dead-end pores and with the minimum reduction of the total void volume. The separation layer of nanofibers has a porosity of over 70% of its volume, whereas the separation layer in conventional ceramic membranes has a porosity below 36% and inevitably includes dead-end pores that make no contribution to the flux. This radical change in membrane texture greatly enhances membrane performance. The resulting membranes were able to filter out 95.3% of 60-nm particles from a 0.01 wt % latex while maintaining a relatively high flux of between 800 and 1000 L/m2.h, under a low driving pressure (20 kPa). Such flow rates are orders of magnitude greater than those of conventional membranes with equal selectivity. Moreover, the flux was stable at approximately 800 L/m2.h with a selectivity of more than 95%, even after six repeated runs of filtration and calcination. Use of different supports, either porous glass or porous alumina, had no substantial effect on the performance of the membranes; thus, it is possible to construct the membranes from a variety of supports without compromising functionality. The Darcy equation satisfactorily describes the correlation between the filtration flux and the structural parameters of the new membranes. The assembly of nanofiber meshes to combine high flux with excellent selectivity is an exciting new direction in membrane fabrication.

Laponite-supported titania photocatalysts.

This study builds on previous results published on the synthesis and characterization of laponite-supported titania photocatalysts. Titania nanocrystals are prepared prior to addition to the clay dispersion, by a sol-gel synthesis incorporating a microwave hydrothermal step. In addition to previously examinations with XRD, TEM, and FT-IR, the samples are further characterized with SEM, 29Si NMR, and BET N2 sorption to gain additional insight into the effect of TiO2 concentration and surface area on the photoactivity of the samples.

Edge-modification of laponite with dimethyl-octylmethoxysilane.

This study examines the edge modification of laponite, with a monoalkoxy silane, dimethyl-octylmethoxysilane. The influence of ultrasonics, aging time and silane concentration on the resultant materials is examined. The silylated clays are characterized by XRD, IES, TGA, and Si NMR. The amount of grafted silane was increased by increasing the ratio of silane to clay, sonication of the reaction mixture and ageing the reaction mixture for no more than 24 h to avoid removal of grafted silane due to equilibrium effects.

Synthesis and characterisation of clay-supported titania photocatalysts.

This study examines the use of laponite, a synthetic smectite, which forms exfoliated silicate layers when dispersed in water, as an inorganic support for titania nanocrystals. Titania nanocrystals are prepared prior to addition to the clay dispersion, by a sol-gel synthesis incorporating a microwave hydrothermal step. The characteristics of the resultant structure such as titania phase, crystallite size, and particulate size are examined via X-ray diffraction (XRD), transmission electron spectroscopy (TEM), and infrared spectroscopy.

Silver and palladium alloy nanoparticle catalysts: reductive coupling of nitrobenzene through light irradiation.

Silver-palladium (Ag-Pd) alloy nanoparticles strongly absorb visible light and exhibit significantly higher photocatalytic activity compared to both pure palladium (Pd) and silver (Ag) nanoparticles. Photocatalysts of Ag-Pd alloy nanoparticles on ZrO2 and Al2O3 supports are developed to catalyze the nitroaromatic coupling to the corresponding azo compounds under visible light irradiation. Ag-Pd alloy NP/ZrO2 exhibited the highest photocatalytic activity for nitrobenzene coupling to azobenzene (yield of ∼80% in 3 hours). The photocatalytic efficiency could be optimized by altering the Ag : Pd ratio of the alloy nanoparticles, irradiation light intensity, temperature and wavelength. The rate of the reaction depends on the population and energy of the excited electrons, which can be improved by increasing the light intensity or by using a shorter wavelength. The knowledge developed in this study may inspire further studies on Ag alloy photocatalysts and organic syntheses using Ag-Pd nanoparticle catalysts driven under visible light Irradiation.

Photon Energy Threshold in Direct Photocatalysis with Metal Nanoparticles: Key Evidence from the Action Spectrum of the Reaction.

By investigating the action spectra (the relationship between the irradiation wavelength and apparent quantum efficiency of reactions under constant irradiance) of a number of reactions catalyzed by nanoparticles including plasmonic metals, nonplasmonic metals, and their alloys at near-ambient temperatures, we found that a photon energy threshold exists in each photocatalytic reaction; only photons with sufficient energy (e.g., higher than the energy level of the lowest unoccupied molecular orbitals) can initiate the reactions. This energy alignment (and the photon energy threshold) is determined by various factors, including the wavelength and intensity of irradiation, molecule structure, reaction temperature, and so forth. Hence, distinct action spectra were observed in the same type of reaction catalyzed by the same catalyst due to a different substituent group, a slightly changed reaction temperature. These results indicate that photon-electron excitations, instead of the photothermal effect, play a dominant role in direct photocatalysis of metal nanoparticles for many reactions.

Discoloration and mineralization of Reactive Red HE-3B by heterogeneous photo-Fenton reaction.

Discoloration and mineralization of Reactive Red HE-3B were studied by using a laponite clay-based Fe nanocomposite (Fe-Lap-RD) as a heterogeneous catalyst in the presence of H2O2 and UV light. Our experimental results clearly indicate that Fe-Lap-RD mainly consists of Fe2O3 (meghemite) and Fe2Si4O10(OH)2 (iron silicate hydroxide) which have tetragonal and monoclinic structures, respectively, and has a high specific surface area (472 m2/g) as well as a high total pore volume (0.547 cm3/g). It was observed that discoloration of HE-3B undergoes a much faster kinetics than mineralization of HE-3B. It was also found that initial HE-3B concentration, H2O2 concentration, UV light wavelength and power, and Fe-Lap-RD catalyst loading are the four main factors that can significantly influence the mineralization of HE-3B. At optimal conditions, complete discoloration of 100 mg/L HE-3B can be achieved in 30 min and the total organic carbon removal ratio can attain 76% in 120 min, illustrating that Fe-Lap-RD has a high photo-catalytic activity in the photo-assisted discoloration and mineralization of HE-3B in the presence of UV light (254 nm) and H2O2.