Ultrathin lanthanide oxides nanomaterials： synthesis, properties and applications

Over the past decade, ultrathin lanthanide oxides （Ln2O3, Ln = La to Lu） nanomaterials have been intensively studied in the fields of rare earth materials science. This unique class of nanomaterials has shown many unprecedented properties （big surface area, high surface effect, physical and chemical activities） and is thus being explored for numerous promising applications. In this review, a brief introduction of ultrathin Ln2O3 nanomaterials was given and their unique advantages were highlighted. Then, the typical synthetic methodologies were summarized and compared （thermal decomposition, solvothermal, soft template, co-precipition and microwave etc.）. Due to the high surface effect, some promising applications of ultmthin Ln203 nanomaterials, such as drug delivery and catalysis of CO oxidation, were reviewed. Finally, on the basis of current achievements on ultrathin Ln203 nanomaterials, personal perspectives and challenges on future research directions were proposed.

Hydrothermal synthesis of lanthanide(hydr)oxide micro/nanorods in presence of tetrabutylammonium hydroxide

Uniform and well-defined lanthanide hydroxide and oxide micro/nanorods Ln（OH）_3（Ln=La, Pr, Sm, Eu, Gd, Er） and Gd（OH）_3：Eu^（3＋）, Gd_2O_3：Eu^（3＋） were successfully synthesized through a green and facile hydrothermal method. Tetrabutylammonium hydroxide（TBAH） and lanthanide nitrides were used as the hydrothermal precursors without the addition of any templates/surfactants. The products were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, high-resolution transmission electron microscopy（HRTEM） and photoluminescence（PL） spectra. The result demonstrated that lanthanide hydroxide micro/nanorods with 20–80 nm in diameter and 50–450 in length were obtained. The size of the Ln（OH）_3（Ln=La, Pr, Sm, Eu, Gd, Er） rods increased with the increase of the atomic number. The size of the Gd（OH）_3：Eu^（3＋） rods decreased with the increase of p H value by modulating the amount of the TBAH solution. The as-formed product via the hydrothermal process, Gd（OH）_3：Eu^（3＋）, could be transformed to Gd_2O_3：Eu^（3＋） with the same morphology and a slight shrinking in size after a post annealing process. It is a facial method to synthesize photoluminescent nanomaterial of Gd_2O_3：Eu^（3＋）. The Gd_2O_3：Eu^（3＋） microrods exhibited strong red emission corresponding to ~5D）0→~7F_2 transition（610 nm） of Eu^（3＋） under UV light excitation（257 nm）.

Methane activation by[LnO]^(+):the 4f orbital matters

Gas-phase reactions of[LnO]^(+)with methane have been studied by using inductively coupled plasma-mass spectrometer(ICP-MS)combined with quantum chemical calculations.Experiments indicate that the[LnO]^(+)(Ln=Sm-Lu)ions are able to activate methane to generate methyl radicals.In particular,[EuO]^(+)and[YbO]^(+)exhibit the highest reactivity.Interestingly,ab initio computations reveal a novel HAT process operating in the absence of a terminal oxygen radical,as mediated by[EuO]^(+)and[YbO]^(+).Such a process diverges from previous findings on the methane activation by metal oxide clusters,not only on the electronic pattern during the course of hydrogen transfer,but also on the important role that 4f electrons play.The associated electronic origins have been discussed,and the well-designed 4f electron occupation may turn to be a promising approach in constructing lanthanide involved catalysts.