Elucidation of a Photothermal Energy Conversion Mechanism in Hydrogenated Molybdenum Suboxide: Interplay of Trapped Charges and Their Dielectric Interactions.

Hydrogenated molybdenum suboxide (HxMoO3-y) is a promising photothermal energy conversion (PEC) material. However, its charge carrier dynamics and underlying mechanisms remain unclear. Utilizing flash-photolysis time-resolved microwave conductivity, we investigated charge carrier-dielectric interactions in the Pt/HxMoO3-y composite. The charge recombination of H2-reduced Pt/HxMoO3-y was 2-3 orders of magnitude faster than that of Pt/MoO3, indicating efficient PEC. A complex photoconductivity study revealed that Pt/HxMoO3-y has two types of trapping mechanisms, Drude-Zener (DZ) and negative permittivity effect (NPE) modes, depending on the reduction temperature. Pt/HxMoO3-y reduced at 100 °C exhibited a dominant NPE owing to the electrical interaction of trapped charges with the surrounding ions and/or OH base. This polaronic trapped state retarded the PEC process. We found Pt/HxMoO3-y reduced at 200 °C to be optimal owing to the balanced suppression of the NPE and charge diffusion. This is the first report revealing the charge dynamics in hydrogenated metal oxides and their impacts on PEC processes.

A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO2 hydrogenation to methanol.

Production of methanol from anthropogenic carbon dioxide (CO2) is a promising chemical process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO2 hydrogenation to methanol, reduction of CO2 to intermediate species is generally considered to be a crucial step. It is of great significance to design and develop advanced heterogeneous catalysts and to engineer the surface structures to promote CO2-to-methanol conversion. We herein report an oxygen-defective molybdenum sub-oxide coupled with Pt nanoparticles (Pt/H x MoO3-y ) which affords high methanol yield with a methanol formation rate of 1.53 mmol g-cat -1 h-1 in liquid-phase CO2 hydrogenation under relatively mild reaction conditions (total 4.0 MPa, 200 °C), outperforming other oxide-supported Pt catalysts in terms of both the yield and selectivity for methanol. Experiments and comprehensive analyses including in situ X-ray absorption fine structure (XAFS), in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and density functional theory (DFT) calculations reveal that both abundant surface oxygen vacancies (VO) and the redox ability of Mo species in quasi-stable H x MoO3-y confer the catalyst with enhanced adsorption and activation capability to subsequently transform CO2 to methanol. Moreover, the Pt NPs act as H2 dissociation sites to regenerate oxygen vacancies and as hydrogenation sites for the CO intermediate to finally afford methanol. Based on the experimental and computational studies, an oxygen-vacancy-mediated "reverse Mars-van Krevelen (M-vK)" mechanism is proposed. This study affords a new strategy for the design and development of an efficient heterogeneous catalyst for CO2 conversion.

One-Day Two-Fraction Radiosurgery for Brain Metastases Using Gamma Knife.

OBJECTIVE: We aimed to evaluate the feasibility of a one-day two-fraction Gamma Knife radiosurgery (GKRS) for brain metastases. CASES AND METHODS: Ten cases with ten brain metastases (four cases of lung adenocarcinoma, one small cell lung carcinoma (SCLC), two renal cell carcinoma, one breast cancer, one esophageal carcinoma, and one bile duct carcinoma) were treated by one-day two-fraction (with an interval of more than six hours) GKRS under rigid skull frame fixation. Of the ten brain metastases, five lesions were in the frontal lobe, one in temporal, one in occipital, and three in the cerebellar hemisphere. The mean planning target volume (PTV) of the ten brain tumors was 7.8 ml (median, 8.0; range, 3.8 - 11.8). The ten targets of the mean prescription isodose volume (PIV) of 10.1 ml (median, 10.1; range, 4.4 - 15.9) were treated with a mean margin dose of 20.4 Gy (median, 20.5; range, 16.4 - 22) in two fractions. In five cases, other small brain metastases (one to seven tumors) were also treated simultaneously in a single fraction GKRS. The indication of two-fraction radiosurgery was large lesion size in eight, retreatment in three, the proximity of the motor area in three, and pre-existing perifocal edema symptom of dysarthria in two, nausea and vomiting in one, and dementia in one. RESULTS: Eight cases were alive at the end of the follow-up period of one to nine months (median, 6). One patient with SCLC died four and a half months after GKRS, from aggressive regrowth of the treated frontal lesion after transient marked shrinkage. Another patient died four months after GKRS due to the progression of other brain tumors treated by single fraction GKRS at the same time. In nine of 10 cases, the size of the treated tumors was controlled until the end of the follow-up period or the patient's death. In two cases, an additional GKRS was performed for newly developed brain metastases at distant locations at six months and five months after one-day two-fraction GKRS, respectively, and controlled at the end of the follow-up period. CONCLUSIONS: A relatively high dose may be safely delivered to large lesions, to those close to the important structures, or those with perifocal edema by one-day two-fraction radiosurgery. Local control was good except for a relapsed SCLC metastasis case. Evaluation in more cases with a longer follow-up period is necessary to determine definite indications and optimal prescription doses.