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.

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.

Surface-Plasmon-Enhanced Transmetalation between Copper and Palladium Nanoparticle Catalyst.

Surface-plasmon-mediated phenylacetylide intermediate transfer from the Cu to the Pd surface affords a novel mechanism for transmetalation, enabling wavelength-tunable cross-coupling and homo-coupling reaction pathway control. C-C bond forming Sonogashira coupling and Glaser coupling reactions in O2 atmosphere are efficiently driven by visible light over heterogeneous Cu and Pd nanoparticles as a mixed catalyst without base or other additives. The reaction pathway can be controlled by switching the excitation wavelength. Shorter wavelengths (400-500 nm) give the Glaser homo-coupling diyne, whereas longer wavelength irradiation (500-940 nm) significantly increases the degree of cross-coupling Sonogashira coupling products. The ratio of the activated intermediates of alkyne to the iodobenzene is wavelength dependent and this regulates transmetalation. This wavelength-tunable reaction pathway is a novel way to optimize the product selectivity in important organic syntheses.

In Situ Atomic-Scale Study on the Ultralarge Bending Behaviors of TiO2-B/Anatase Dual-Phase Nanowires.

It is challenging but important to understand the mechanical properties of one-dimensional (1D) nanomaterials for their design and integration into nanodevices. Generally, brittle ceramic nanowires (NWs) cannot withstand a large bending strain. Herein, in situ bending deformation of titanium dioxide (TiO2) NWs with a bronze/anatase dual-phase was carried out inside a transmission electron microscopy (TEM) system. An ultralarge bending strain up to 20.3% was observed on individual NWs. Through an in situ atomic-scale study, the large bending behavior for a dual-phase TiO2 NW was found to be related to a continuous crystalline-structure evolution including phase transition, small deformation twinning, and dislocation nucleation and movements. Additionally, no amorphization or crack occurred in the dual-phase TiO2 NW even under an ultralarge bending strain. These results revealed that an individual ceramic NW can undergo a large bending strain with rich defect activities.

Utilizing a Photocatalysis Process to Achieve a Cathode with Low Charging Overpotential and High Cycling Durability for a Li-O2 Battery.

The practical applications of non-aqueous lithium-oxygen batteries are impeded by large overpotentials and unsatisfactory cycling durability. Reported here is that commonly encountered fatal problems can be efficiently solved by using a carbon- and binder-free electrode of titanium coated with TiO2 nanotube arrays (TNAs) and gold nanoparticles (AuNPs). Ultraviolet irradiation of the TNAs generates positively charged holes, which efficiently decompose Li2 O2 and Li2 CO3 during recharging, thereby reducing the overpotential to one that is near the equilibrium potential for Li2 O2 formation. The AuNPs promote Li2 O2 formation, resulting in a large discharge capacity. The electrode exhibits excellent stability with about 100 % coulombic efficiency during continuous cycling of up to 200 cycles, which is due to the carbon- and binder-free composition. This work reveals a new strategy towards the development of highly efficient oxygen electrode materials for lithium-oxygen batteries.

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.

Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid Using O2 and a Photocatalyst of Co-thioporphyrazine Bonded to g-C3N4.

Selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is one of the key reactions for producing chemical commodities from biomass and their derivatives. The challenge for this reaction is to develop an efficient catalytic process that can be conducted under mild conditions (room temperature and atmospheric pressure, using oxygen molecules in air as the oxidant) and a recyclable catalyst. Herein we report a photocatalyst of cobalt thioporphyrazine (CoPz) dispersed on g-C3N4 (abbreviated as CoPz/g-C3N4), which exhibits excellent catalytic activity toward the selective oxidation of HMF into FDCA under simulated sunlight using oxygen molecules in air as a benign oxidant. For example, an FDCA yield of 96.1% in an aqueous solution at pH = 9.18 is achieved at ambient temperature and air pressure. At lower pH (4.01), the product generated is 2,5-diformylfuran. Hence, it is possible to control the reaction outcome by control of the pH of the reaction system. g-C3N4 itself is not a suitable catalyst for the selective oxidation because under the experimental conditions g-C3N4 generates hydroxyl radicals that initiate processes that oxidize HMF directly to CO2 and H2O. CoPz on the other hand activates O2 to give singlet oxygen (1O2), which more controllably oxidizes HMF to FDCA albeit at a more moderate yield (36.2%). The strong interaction between the CoPz and g-C3N4 in the CoPz/g-C3N4 catalyst is experimentally evidenced, which not only improves accessibility of the CoPz sites and makes the catalyst recyclable but also disables the hydroxyl radical generation by g-C3N4 and promotes 1O2 generation on the CoPz sites, significantly enhancing the catalytic performance. This study demonstrates the potential for efficient non-noble metal photocatalysts for organic transformations driven by sunlight.

Catalytic transformation of aliphatic alcohols to corresponding esters in O2 under neutral conditions using visible-light irradiation.

Selective oxidation of aliphatic alcohols under mild and base-free conditions is a challenging process for organic synthesis. Herein, we report a one-pot process for the direct oxidative esterification of aliphatic alcohols that is significantly enhanced by visible-light irradiation at ambient temperatures. The new methodology uses heterogenerous photocatalysts of gold-palladium alloy nanoparticles on a phosphate-modified hydrotalcite support and molecular oxygen as a benign oxidant. The alloy photocatalysts can absorb incident light, and the light-excited metal electrons on the surface of metal nanoparticles can activate the adsorbed reactant molecules. Tuning the light intensity and wavelength of the irradiation can remarkably change the reaction activity. Shorter wavelength light (<550 nm) drives the reaction more efficiently than light of longer wavelength (e.g., 620 nm), especially at low temperatures. The phosphate-exchanged hydrotalcite support provides sufficient basicity (and buffer) for the catalytic reactions; thus, the addition of base is not required. The photocatalysts are efficient and readily recyclable. The findings reveal the first example of using "green" oxidants and light energy to drive direct oxidative esterification of aliphatic alcohols under base-free, mild conditions.

Visible light induced green transformation of primary amines to imines using a silicate supported anatase photocatalyst.

Catalytic oxidation of amine to imine is of intense present interest since imines are important intermediates for the synthesis of fine chemicals, pharmaceuticals, and agricultural chemicals. However, considerable efforts have been made to develop efficient methods for the oxidation of secondary amines to imines, while little attention has until recently been given to the oxidation of primary amines, presumably owing to the high reactivity of generated imines of primary amines that are easily dehydrogenated to nitriles. Herein, we report the oxidative coupling of a series of primary benzylic amines into corresponding imines with dioxygen as the benign oxidant over composite catalysts of TiO2 (anatase)-silicate under visible light irradiation of λ > 460 nm. Visible light response of this system is believed to be as a result of high population of defects and contacts between silicate and anatase crystals in the composite and the strong interaction between benzylic amine and the catalyst. It is found that tuning the intensity and wavelength of the light irradiation and the reaction temperature can remarkably enhance the reaction activity. Water can also act as a green medium for the reaction with an excellent selectivity. This report contributes to the use of readily synthesized, environmentally benign, TiO2 based composite photocatalyst and solar energy to realize the transformation of primary amines to imine compounds.

ortho-Dihydroxyl-9,10-anthraquinone dyes as visible-light sensitizers that exhibit a high turnover number for hydrogen evolution.

Pt/TiO2 sensitized by the cheap and organic ortho-dihydroxyl-9,10-anthraquinone dyes, such as Alizarin and Alizarin Red, achieved a TON of approximately 10 000 (TOF > 250 h(-1) for the first ten hours) during >80 hours of visible light irradiation (>420 nm) for photocatalytic hydrogen evolution when triethanolamine was used as the sacrificial donor. The stability and activity enhancements can be attributed to the two highly serviceable redox reactions involving the 9,10-dicarbonyl and ortho-dihydroxyl groups of the anthracene ring, respectively.

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.

Facile synthesis of Bi3O(OH)(AsO4)2 and simultaneous photocatalytic oxidation and adsorption of Sb(III) from wastewater.

Antimony (Sb) decontamination in water is necessary owing to the worsening pollution which seriously threatens human life safety. Designing bismuth-based photocatalysts with hydroxyls have attracted growing interest because of the broad bandgap and enhanced separation efficiency of photogenerated electron/hole pairs. Until now, the available photocatalysis information regarding bismuth-based photocatalysts with hydroxyls has remained scarce and the contemporary report has been largely limited to Bi3O(OH)(PO4)2 (BOHP). Herein, Bi3O(OH)(AsO4)2 (BOHAs), a novel ultraviolet photocatalyst, was fabricated via the co-precipitation method for the first time, and developed to simultaneous photocatalytic oxidation and adsorption of Sb(III). The rate constant of Sb(III) removal by the BOHAs was 32.4, 3.0, and 4.3 times higher than those of BiAsO4, BOHP, and TiO2, respectively, indicating that the introduction of hydroxyls could increase the removal of Sb(III). Additionally, the crucial operational parameters affecting the adsorption performance (catalyst dosage, concentration, pH, and common anions) were investigated. The BOHAs maintained 85% antimony decontamination of the initial yield after five successive cycles of photocatalysis. The Sb(III) removal involved photocatalytic oxidation of adsorbed Sb(III) and subsequent adsorption of the yielded Sb(V). With the acquired knowledge, we successfully applied the photocatalyst for antimony removal from industrial wastewater. In addition, BOHAs could also be powerful photocatalysts in the photodegradation of organic pollutants studies of which are ongoing. It reveals an effective strategy for synthesizing bismuth-based photocatalysts with hydroxyls and enhancing pollutants' decontamination.

Enhancing catalytic performance of palladium in gold and palladium alloy nanoparticles for organic synthesis reactions through visible light irradiation at ambient temperatures.

The intrinsic catalytic activity of palladium (Pd) is significantly enhanced in gold (Au)-Pd alloy nanoparticles (NPs) under visible light irradiation at ambient temperatures. The alloy NPs strongly absorb light and efficiently enhance the conversion of several reactions, including Suzuki-Miyaura cross coupling, oxidative addition of benzylamine, selective oxidation of aromatic alcohols to corresponding aldehydes and ketones, and phenol oxidation. The Au/Pd molar ratio of the alloy NPs has an important impact on performance of the catalysts since it determines both the electronic heterogeneity and the distribution of Pd sites at the NP surface, with these two factors playing key roles in the catalytic activity. Irradiating with light produces an even more profound enhancement in the catalytic performance of the NPs. For example, the best conversion rate achieved thermally at 30 °C for Suzuki-Miyaura cross coupling was 37% at a Au/Pd ratio of 1:1.86, while under light illumination the yield increased to 96% under the same conditions. The catalytic activity of the alloy NPs depends on the intensity and wavelength of incident light. Light absorption due to the Localized Surface Plasmon Resonance of gold nanocrystals plays an important role in enhancing catalyst performance. We believe that the conduction electrons of the NPs gain the light absorbed energy producing energetic electrons at the surface Pd sites, which enhances the sites' intrinsic catalytic ability. These findings provide useful guidelines for designing efficient catalysts composed of alloys of a plasmonic metal and a catalytically active transition metal for various organic syntheses driven by sunlight.

Tuning the surface structure of nitrogen-doped TiO2 nanofibres--an effective method to enhance photocatalytic activities of visible-light-driven green synthesis and degradation.

Nitrogen-doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400-700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N-doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface-bonded N species, whereas the core remains N doped. N-Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible-light irradiation. The surface-oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N-doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N-doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible-light-driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N-doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N-doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.

Enhancing photoactivity of TiO2(B)/anatase core-shell nanofibers by selectively doping cerium ions into the TiO2(B) core.

Cerium ions (Ce(3+)) can be selectively doped into the TiO2(B) core of TiO2(B)/anatase core-shell nanofibers by means of a simple one-pot hydrothermal treatment of a starting material of hydrogen trititanate (H2Ti3O7) nanofibers. These Ce(3+) ions (≈0.202 nm) are located on the (110) lattice planes of the TiO2(B) core in tunnels (width≈0.297 nm). The introduction of Ce(3+) ions reduces the defects of the TiO2(B) core by inhibiting the faster growth of (110) lattice planes. More importantly, the redox potential of the Ce(3+)/Ce(4+) couple (E°(Ce(3+)/Ce(4+))=1.715 V versus the normal hydrogen electrode) is more negative than the valence band of TiO2(B). Therefore, once the Ce(3+)-doped nanofibers are irradiated by UV light, the doped Ce(3+) ions--in close vicinity to the interface between the TiO2(B) core and anatase nanoshell--can efficiently trap the photogenerated holes. This facilitates the migration of holes from the anatase shell and leaves more photogenerated electrons in the anatase nanoshell, which results in a highly efficient separation of photogenerated charges in the anatase nanoshell. Hence, this enhanced charge-separation mechanism accelerates dye degradation and alcohol oxidation processes. The one-pot treatment doping strategy is also used to selectively dope other metal ions with variable oxidation states such as Co(2+/3+) and Cu(+/2+) ions. The doping substantially improves the photocatalytic activity of the mixed-phase nanofibers. In contrast, the doping of ions with an invariable oxidation state, such as Zn(2+), Ca(2+), or Mg(2+), does not enhance the photoactivity of the mixed-phase nanofibers as the ions could not trap the photogenerated holes.

Insight on the heterogeneously activated H2O2 with goethite under visible light for cefradine degradation: pH dependence and photoassisted effect.

The iron mineral-catalyzed degradation of cephalosporin antibiotics with H2O2 occurs ubiquitously in nature. Despite numerous studies, the effects of environmental conditions on reactive species production and degradation processes of cephalosporins remain unclear. Here, we report the iron mineral of goethite as the efficient and heterogenous catalyst for the degradation of cefradine (CRD) via H2O2 activation under different conditions involving pH and visible light irradiation. Results show that the CRD removal rate is highly dependent on pH and visible light irradiation. Interestingly, when the pH ranges from 4.0 to 7.0, the degradation intermediates of CRD under dark are the same as under visible light conditions in the goethite/H2O2 system. And, the ratio of CRD degradation rate constant (kLight/kDark) reaches a maximum at pH 5.0, suggesting that CRD existing as zwitterion species is preferable for its removal with photoassistance. The mechanism investigation reveals that both •OH and ≡[FeIVO]2+ oxidants are generated during the reaction process, and •OH is the major oxidant at acidic pH, while ≡[FeIVO]2+ is more likely to be formed with photoassistance at near-neutral pH. According to UPLC-MS/MS analysis, CRD degradation likely happens via hydrogen atom abstraction from cyclohexadienyl by •OH, thioether and olefin oxidation by ≡[FeIVO]2+, and FeIII-catalyzed hydrolytic cleavage of ß-lactam ring. These findings highlight the vital roles of pH and photoassistance in the heterogeneously activated H2O2 with goethite for CRD degradation.

Iron redox cycling in layered clay minerals and its impact on contaminant dynamics: A review.

A majority of clay minerals contain Fe, and the redox cycling of Fe(III)/Fe(II) in clay minerals has been extensively studied as it may fuel the biogeochemical cycles of nutrients and govern the mobility, toxicity and bioavailability of a number of environmental contaminants. There are three types of Fe in clay minerals, including structural Fe sandwiched in the lattice of clays, Fe species in interlayer space and adsorbed on the external surface of clays. They exhibit distinct reactivity towards contaminants due to their differences in redox properties and accessibility to contaminant species. In natural environments, microbially driven Fe(III)/Fe(II) redox cycling in clay minerals is thought to be important, whereas reductants (e.g., dithionite and Fe(II)) or oxidants (e.g., peroxygens) are capable of enhancing the rates and extents of redox dynamics in engineered systems. Fe(III)-containing clay minerals can directly react with oxidizable pollutants (e.g., phenols and polycyclic aromatic hydrocarbons (PAHs)), whereas structural Fe(II) is able to react with reducible pollutants, such as nitrate, nitroaromatic compounds, chlorinated aliphatic compounds. Also structural Fe(II) can transfer electrons to oxygen (O2), peroxymonosulfate (PMS), or hydrogen peroxide (H2O2), yielding reactive radicals that can promote the oxidative transformation of contaminants. This review summarizes the recent discoveries on redox reactivity of Fe in clay minerals and its links to fates of environmental contaminants. The biological and chemical reduction mechanisms of Fe(III)-clay minerals, as well as the interaction mechanism between Fe(III) or Fe(II)-containing clay minerals and contaminants are elaborated. Some knowledge gaps are identified for better understanding and modelling of clay-associated contaminant behavior and effective design of remediation solutions.

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.