Ingenieria e Investigacion

Denosumab Prevents Bone Loss and Microarchitectural Deterioration in Premenopausal Women With Breast Cancer Receiving Estradiol Suppression Therapy: A Randomized Controlled Trial
Ramchand SK, Ghasem-Zadeh A, Hoermann R, White S, Yeo B, Francis PA, Xu CLH, Coleman O, Shore-Lorenti C, Ebeling PR, Zajac JD, Seeman E and Grossmann M
Suppression of ovarian function and aromatase inhibition (AI) increases disease-free survival in premenopausal women with estrogen receptor (ER)-positive early-stage breast cancer but accelerates bone loss. We therefore hypothesized that suppressing bone remodeling using denosumab (DMAB) would prevent bone loss in these women.
Efficient CuO Photocathodes for Aqueous Photoelectrochemical CO Reduction to Formate and Syngas
Xia M, Pan L, Liu Y, Gao J, Li J, Mensi M, Sivula K, Zakeeruddin SM, Ren D and Grätzel M
Photoelectrochemical carbon dioxide reduction (PEC-COR) represents a promising approach for producing renewable fuels and chemicals using solar energy. However, attaining even modest solar-to-fuel (STF) conversion efficiency often necessitates the use of costly semiconductors and noble-metal catalysts. Herein, we present a CuO/GaO/TiO photocathode modified with Sn/SnO catalysts through a simple photoelectrodeposition method. It achieves a remarkable half-cell STF efficiency of ∼0.31% for the COR in aqueous KHCO electrolyte, under AM 1.5 G illumination. The system enables efficient production of syngas (FE: ∼62%, CO/H ≈ 1:2) and formate (FE: ∼38%) with a consistent selectivity over a wide potential range, from +0.34 to -0.16 V vs the reversible hydrogen electrode. We ascribe the observed performance to the favorable optoelectronic characteristics of our CuO heterostructure and the efficient Sn/SnO catalysts incorporated in the PEC-COR reactions. Through comprehensive experimental investigations, we elucidate the indispensable role of CuO buried p-n junctions in generating a high photovoltage (∼1 V) and enabling efficient bulk charge separation (up to ∼70% efficiency). Meanwhile, we discover that the deposited Sn/SnO catalysts have critical dual effects on the overall performance of the PEC devices, serving as active COR catalysts as well as the semiconductor front contact. It could facilitate interfacial electron transfer between the catalysts and the semiconductor device for COR by establishing a barrier-free ohmic contact.
Electrochemical synthesis of propylene from carbon dioxide on copper nanocrystals
Gao J, Bahmanpour A, Kröcher O, Zakeeruddin SM, Ren D and Grätzel M
The conversion of carbon dioxide to value-added products using renewable electricity would potentially help to address current climate concerns. The electrochemical reduction of carbon dioxide to propylene, a critical feedstock, requires multiple C-C coupling steps with the transfer of 18 electrons per propylene molecule, and hence is kinetically sluggish. Here we present the electrosynthesis of propylene from carbon dioxide on copper nanocrystals with a peak geometric current density of -5.5 mA cm. The metallic copper nanocrystals formed from CuCl precursor present preponderant Cu(100) and Cu(111) facets, likely to favour the adsorption of key *C and *C intermediates. Strikingly, the production rate of propylene drops substantially when carbon monoxide is used as the reactant. From the electrochemical reduction of isotope-labelled carbon dioxide mixed with carbon monoxide, we infer that the key step for propylene formation is probably the coupling between adsorbed/molecular carbon dioxide or carboxyl with the *C intermediates that are involved in the ethylene pathway.
Solar reduction of carbon dioxide on copper-tin electrocatalysts with energy conversion efficiency near 20
Gao J, Li J, Liu Y, Xia M, Finfrock YZ, Zakeeruddin SM, Ren D and Grätzel M
Copper catalysts modified with tin have been demonstrated to be selective for the electroreduction of carbon dioxide to carbon monoxide. However, such catalysts require the precise control of tin loading amount. Here, we develop a copper/tin-oxide catalyst with dominant tin oxide surface being formed via a spontaneous exchange reaction between sputtered tin and copper oxide. Even though the surface of this catalyst is tin-rich, it achieves an excellent performance towards carbon monoxide production in a flow cell. This contrasts with copper/tin-oxide prepared via atomic layer deposition since it yields selectivity towards carbon monoxide only on a copper-rich surface. Mechanism studies reveal that the tin sites on the tin-rich copper/tin-oxide surface achieve a suitable binding with adsorbed carbon monoxide under the presence of copper. Powered by a triple-junction solar cell, the copper/tin-oxide based electrolyzer sets a new benchmark solar-to-chemical energy conversion efficiency of 19.9 percent with a Faradaic efficiency of 98.9 percent towards carbon monoxide under simulated standard air mass 1.5 global illumination.
Revisiting the Impact of Morphology and Oxidation State of Cu on CO Reduction Using Electrochemical Flow Cell
Asiri AM, Gao J, Khan SB, Alamry KA, Marwani HM, Khan MSJ, Adeosun WA, Zakeeruddin SM, Ren D and Grätzel M
Electroreduction of carbon dioxide (CO) in a flow electrolyzer represents a promising carbon-neutral technology with efficient production of valuable chemicals. In this work, the catalytic performance of polycrystalline copper (Cu), CuO-derived copper (O(I)D-Cu), and CuO-derived copper (O(II)D-Cu) toward CO reduction is unraveled in a custom-designed flow cell. A peak Faradaic efficiency of >70% and a production rate of ca. -250 mA cm toward C products have been achieved on all the catalysts. In contrast to previous studies that reported a propensity for C products on OD-Cu in conventional H-cells, the selectivity and activity of ethylene-dominated C products are quite similar on the three types of catalysts at the same current density in our flow reactor. Our analysis also reveals current density to be a critical factor determining the C-C coupling in a flow cell, regardless of Cu catalyst's initial oxidation state and morphology.