A new biomimetic heterogeneous photocatalyst ([FeFe]@ZrPF) has been synthesized through the incorporation of homogeneous complex 1 [(í-SCH2)2NC(O)C5H4N]-[Fe2(CO)6] into the highly robust zirconium-porphyrin based metal-organic framework (ZrPF). The immobilized biomimetic [Fe2S2] catalyst inside the MOF shows great improvement in hydrogen generation compared to the reference homogeneous catalyst complex 1.

High-silica zeolites, as exemplified by ZSM-5, with excellent chemical and thermal stability, have generated a revolution in industrial catalysis. In contrast, prior to this work, high-silica-zeolite-like chalcogenides based on germanium/tin remained unknown, even after decades of research. Here six crystalline high-germanium or high-tin zeolite-type sulfides and selenides with four different topologies are reported. Their unprecedented framework compositions give these materials much improved thermal and chemical stability with high surface area (Langmuir surface area of 782 m(2)/g(-1)) comparable to or better than zeolites. Among them, highly stable CPM-120-ZnGeS allows for ion exchange with diverse metal or complex cations, resulting in fine-tuning in porosity, fast ion conductivity, and photoelectric response. Being among the most porous crystalline chalcogenides, CPM-120-ZnGeS (exchanged with Cs(+) ions) also shows reversible adsorption with high capacity and affinity for CO2 (98 and 73 cm(3) g(-1) at 273 and 298 K, respectively, isosteric heat of adsorption = 40.05 kJ mol(-1)). Moreover, CPM-120-ZnGeS could also function as a robust photocatalyst for water reduction to generate H2. The overall activity of H2 production from water, in the presence of Na2S-Na2SO3 as a hole scavenger, was 200 μmol h(-1)/(0.10 g). Such catalytic activity remained undiminished under illumination by UV light for as long as measured (200 h), demonstrating excellent resistance to photocorrosion even under intense UV radiation.

We demonstrate an additive manufacturing approach to produce gradient refractive index glass optics. Using direct ink writing with an active inline micromixer, we three-dimensionally print multimaterial green bodies with compositional gradients, consisting primarily of silica nanoparticles and varying concentrations of titania as the index-modifying dopant. The green bodies are then consolidated into glass and polished, resulting in optics with tailored spatial profiles of the refractive index. We show that this approach can be used to achieve a variety of conventional and unconventional optical functions in a flat glass component with no surface curvature.

Self-doped TiO2 shows visible light photocatalytic activity, while commercial TiO2 (P25) is only UV responsive. The incorporation of Ti(3+) into TiO2 structures narrows the band gap (2.90 eV), leading to significantly increased photocatalytic activity for the reduction of CO2 into a renewable hydrocarbon fuel (CH4) in the presence of water vapour under visible light irradiation.

Direct ink writing (DIW) three-dimensional (3D) printing provides a revolutionary approach to fabricating components with gradients in material properties. Herein, we report a method for generating colloidal germania feedstock and germania–silica inks for the production of optical quality germania–silica (GeO2–SiO2) glasses by DIW, making available a new material composition for the development of multimaterial and functionally graded optical quality glasses and ceramics by additive manufacturing. Colloidal germania and silica particles are prepared by a base-catalyzed sol–gel method and converted to printable shear-thinning suspensions with desired viscoelastic properties for DIW. The volatile solvents are then evaporated, and the green bodies are calcined and sintered to produce transparent, crack-free glasses. Chemical and structural evolution of GeO2–SiO2 glasses is confirmed by nuclear magnetic resonance, X-ray diffraction, and Raman spectroscopy. UV–vis transmission and optical homogeneity measurements reveal comparable performance of the 3D printed GeO2–SiO2 glasses to glasses produced using conventional approaches and improved performance over 3D printed TiO2–SiO2 inks. Moreover, because GeO2–SiO2 inks are compatible with DIW technology, they offer exciting options for forming new materials with patterned compositions such as gradients in the refractive index that cannot be achieved with conventional manufacturing approaches.

Open framework metal chalcogenides are a family of porous semiconducting materials with diverse chemical compositions. Here we show that these materials containing covalent three-dimensional superlattices of nanosized supertetrahedral clusters can function as efficient photocatalysts for the reduction of CO2 to CH4. Unlike dense semiconductors, metal cations are successfully incorporated into the channels of the porous semiconducting materials to further tune the physical properties of the materials such as electrical conductivity and band gaps. In terms of the photocatalytic properties, the metal-incorporated porous chalcogenides demonstrated enhanced solar energy absorption and higher electrical conductivity and improved photocatalytic activity.

Kinetic and structural studies have shown that peroxidases are capable of the oxidation of 2,4,6-trichlorophenol (2,4,6-TCP) to 2, 6-dichloro-1,4-benzoquinone (2,6-DCQ). Further reactions of 2,6-DCQ in the presence of H 2 O 2 and OH À yield 2,6-dichloro-3-hydroxy-1,4-benzoquinone (2,6-DCQOH). The reactions of 2,6-DCQ have been monitored spectroscopically [UVÀvisible and electron spin resonance (ESR)] and chromatographically. The hydroxylation product, 2,6-DCQOH, has been observed by UVÀvisible and characterized structurally by 1 H and 13 C NMR spectroscopy. The results are consistent with a nonphotochemical base-catalyzed oxidation of 2,6-DCQ at pH > 7. Because H 2 O 2 is present in peroxidase reaction mixtures, there is also a potential role for the hydrogen peroxide anion (HOO À ). However, in agreement with previous work, we observe that the nonphotochemical epoxidation by H 2 O 2 at pH < 7 is immeasurably slow. Both room-temperature ESR and rapid-freeze-quench ESR methods were used to establish that the dominant nonphotochemical mechanism involves formation of a semiquinone radical (base -catalyzed pathway), rather than epoxidation (direct attack by H 2 O 2 at low pH). Analysis of the kinetics using an Arrhenius model permits determination of the activation energy of hydroxylation (E a = 36 kJ/mol), which is significantly lower than the activation energy of the peroxidase-catalyzed oxidation of 2,4,6-TCP (E a = 56 kJ/mol). However, the reaction is second order in both 2,6-DCQ and OH À so that its rate becomes significant above 25 °C due to the increased rate of formation of 2,6-DCQ that feeds the second-order process. The peroxidase used in this study is the dehaloperoxidase-hemoglobin (DHP A) from Amphitrite ornata, which is used to study the effect of a catalyst on the reactions. The control experiments and precedents in studies of other peroxidases lead to the conclusion that hydroxylation will be observed following any process that leads to the formation of the 2,6-DCQ at pH > 7, regardless of the catalyst used in the 2,4,6-TCP oxidation reaction.

Dissolved silica is ubiquitous in impaired waters, a fouling agent in desalination membranes, resistant to existing antiscalants, and difficult to remove from power plant feed waters, thereby inhibiting long term reuse of industrial water. Herein we report a systematic materials study of an inorganic anion exchanger, hydrotalcite (HTC, (Mg 6 Al 2 (OH) 16 (CO 3)•4H 2 O)), for the highly selective removal of silica from aqueous solutions. HTCs exist in two different forms: crystalline uncalcined and calcined (550 °C) phases. Variables studied in ion-exchange studies include pH, HTC concentration, duration and selectivity with competing anions. Results indicate calcined HTC effectively removes silicate anion from different waters including simulated concentrated cooling tower water (CCTW), and waters with high concentration of competing ions, such as SO 4 2and Cl-. The non-optimized HTC can be easily regenerated and recycled. Calcined HTC has a silica adsorption capacity of 45 mg SiO 2 /g HTC. The single path flow through (SPFT) studies indicate that using ~1.1g /L calcined HTC effectively removes >90% of the dissolved silica from the CCTW. A pseudo-second order kinetic model was fit the experimental data of calcined HTC. Data is supported by Fourier transform infrared (FTIR), Thermogravimetric-Mass analyses (TGA-MS), Energy dispersive spectroscopy (EDS) and powder X-ray diffraction (XRD).