Selective synthesis and shape-dependent photoluminescence properties of (Y_(0.95)Eu_(0.05))_2O_3 submicron spheres and microplates

Red-emission （Y0.95Eu0.05）2O3 submicron spheres and microplates were selectively obtained via hydrothermal precursor synthesis （150 °C, 12 h） followed by calcination at 1000 °C. Characterizations of the products were carried out by combined means of XRD, FT-IR, FE-SEM and PL analysis. The precursors could be modulated from basic-carbonate submicron spheres to normal carbonate microplates by increasing the molar ratio of urea to Y＋Eu from 10 to 40-100. The resultant oxides largely retain their respective precursor morphologies at 1000 °C, but morphology confined crystal growth was observed for the microplates, yielding more enhanced exposure of the （400） facets. Both the （Y0.95Eu0.05）2O3 spheres and microplates exhibit nearly identical positions of the PL bands and similar asymmetry factors of luminescence [I（5D0→7F2）/I（5D0→7F1）, ～11] under 250 nm excitation, but the microplates show a significantly strong red emission at ～613 nm （ ～1.33 times that of the spheres） owing to their larger particle size and denser packing of primary phosphor crystallites.

Morphology-dependent activation of hydrogen peroxide with Cu_(2)O for tetracycline hydrochloride degradation in bicarbonate aqueous solution

The design of efficient heterogeneous catalysts in bicarbonate-activated hydrogen peroxide systems(BAP)is a hot topic in wastewater treatment.In this work,Cu_(2)O nanoparticles with different morphologies including cubic shape(c-Cu_(2)O),octahedron shape(o-Cu_(2)O)and spherical shape(s-Cu_(2)O),were applied in BAP for the first time to degrade tetracycline hydrochloride(TC).Compared with Cu^(2+)ions and CuO,TC degradation was boosted in the presence of Cu_(2)O in the BAP system,with the degradation rate following the order c-Cu_(2)O>o-Cu_(2)O>s-Cu_(2)O.The morphology-dependent effects could be linearly correlated with the ratio of surface oxygen species(O_S),but not with the surface area or Cu(Ⅰ)ratio.The c-Cu_(2)O catalyst with exposure of(100)facets contained 76.6%O_Sas the active site for H_(2)O_(2)adsorption and activation,while the value was much lower for o-Cu_(2)O and s-Cu_(2)O with dominant(111)facets.The presence of HCO_(3)-enhanced the interactions among Cu_(2)O,H_(2)O_(2)and TC,leading to facile oxidation of Cu(Ⅰ)to Cu(Ⅱ)by H_(2)O_(2),and the formation of various reactive species such as hydroxyl radicals and Cu(Ⅲ)contributed to TC degradation.This work provides a new method for enhancing H_(2)O_(2)activation with heterogeneous catalysts by crystal facet engineering.

Morphology-dependent nanocatalysis on metal oxides

The design and fabrication of solid nanomaterials are the key issues in heterogeneous catalysis to achieve desired performance. Traditionally, the main theme is to reduce the size of the catalyst particles as small as possible for maximizing the number of active sites. In recent years, the rapid advancement in materials science has enabled us to fabricate catalyst particles with tuna- ble morphology. Consequently, both size modulation and morphology control of the catalyst particles can be achieved inde- pendently or synergistically to optimize their catalytic properties. In particular, morphology control of solid catalyst particles at the nanometer level can selectively expose the reactive crystal facets, and thus drastically promote their catalytic performance. In this review, we summarize our recent work on the morphology impact of Co304, CeO2 and Fe203 nanomaterials in catalytic reactions, together with related literature on morphology-dependent nanocatalysis of metal oxides, to demonstrate the importance of tuning the shape of oxide-nanocatalysts for prompting their activity, selectivity and stability, which is a rapidly growing topic in heterogeneous catalysis. The fundamental understanding of the active sites in morphology-tunable oxides that are enclosed by reactive crystal facets is expected to direct the development of highly efficient nanocatalysts.

Co_3O_4 nanosheets:synthesis and catalytic application for CO oxidation at room temperature

Hexagonal β-Co(OH)2 nanosheets with edge length of 50 nm and thickness of 10 nm were hydrothermally synthesized with the aid of triethylamine.Upon calcination at 350°C in air,the β-Co(OH)2 nanosheets was converted into Co3O4 nanosheets with a similar dimension.Structural analyses during the calcination process identified that the β-Co(OH)2 precursor was initially dehydrated to HCoO2 and subsequently transferred into Co3O4.When being applied to catalyze CO oxidation at room temperature,the Co3O4 nanosheets exhibited a higher activity than the conventional spherical nanoparticles.This was perhaps related to the partial exposure of the{112}planes over the Co3O4 nanosheets.The porous structure generated during the calcination process also provided significant amounts of surface defects,which might contribute to the enhanced catalytic activity as well.

Morphology-controlled porphyrin nanocrystals with enhanced photocatalytic hydrogen production

Molecular self-assembly is a natured-inspired strategy to integrate individual functional molecules into supramolecular nanostructured materials through noncovalent bond interactions for solar to fuel conversion.However,the design and engineering of the morphology,size,and orderly stacking of supramolecular nanostructures remain a great challenge.In this study,regular porphyrin nanocrystals with different orderly stacked structures are synthesized through noncovalent self-assembly of Pt(II)meso-tetra(4-carboxyphenyl)porphine(PtTCPP),using surfactants with different electronegativity.The synergy of noncovalent bond interactions between porphyrin molecules,and between porphyrin molecules and surfactants resulted in different molecular packing patterns.Due to the spatial ordering of PtTCPP molecules,the different nanocrystals exhibit both collective optical properties and morphology-dependent activities in photocatalytic hydrogen production.The measurements of the photodeposition of dual cocatalysts showed that the photogenerated electrons and holes selectively aggregated at different active sites,revealing separation pathways and directional transfer of photogenerated electrons and holes in the assemblies.This study provides a new strategy to exert rational control over porphyrin self-assembly nanocrystals for highly efficient water splitting.