Abstract Metal promotion could unlock high performance in zinc-zirconium catalysts, ZnZrO x , for CO 2 hydrogenation to methanol. Still, with most efforts devoted to costly palladium, the optimal ...metal choice and necessary atomic-level architecture remain unclear. Herein, we investigate the promotion of ZnZrO x catalysts with small amounts (0.5 mol%) of diverse hydrogenation metals (Re, Co, Au, Ni, Rh, Ag, Ir, Ru, Pt, Pd, and Cu) prepared via a standardized flame spray pyrolysis approach. Cu emerges as the most effective promoter, doubling methanol productivity. Operando X-ray absorption, infrared, and electron paramagnetic resonance spectroscopic analyses and density functional theory simulations reveal that Cu 0 species form Zn-rich low-nuclearity CuZn clusters on the ZrO 2 surface during reaction, which correlates with the generation of oxygen vacancies in their vicinity. Mechanistic studies demonstrate that this catalytic ensemble promotes the rapid hydrogenation of intermediate formate into methanol while effectively suppressing CO production, showcasing the potential of low-nuclearity metal ensembles in CO 2 -based methanol synthesis.
La presente investigación tiene como objetivo analizar el nivel de correlación entre la formación profesional del docente de la escuela de ciencias sociales y administrativas (ECSA) de la UDO Núcleo ...de Monagas, en el periodo 2015 – 2020 y los beneficios otorgados por la III Convención Colectiva Única (CCU) de Trabajadores para el Sector Universitario. Es una investigación de tipo correlacional, tomando como población los 149 docentes adscritos a la escuela de ciencias sociales y administrativas (ECSA) de la Universidad de Oriente Núcleo Monagas. En la investigación se concluye que existe una correlación positiva débil entre las variables Formación Profesional (trabajo de ascenso y estudios de posgrados) y la III Convención Colectiva. Se puede inferir que los docentes se preocupan por su formación profesional siguiendo lo establecido en la Gaceta 70 de la UDO y su reglamento de personal docente y de investigación, y no lo hacen por el beneficio socioeconómico poco significativos que reciben de la III Convención Colectiva.
Methanol Synthesis
In article number 2204122, Javier Pérez‐Ramírez and co‐workers apply flame spray pyrolysis to design superior ZnZrOx catalysts for methanol synthesis from CO2. ...Synthesis‐structure‐performance relationships are established, revealing that zinc speciation and location determine catalyst architecture, the nature of catalytic ensembles, and the corresponding reactivity.
Abstract
Mixed zinc‐zirconium oxides, ZnZrO
x
, are highly selective and stable catalysts for CO
2
hydrogenation to methanol, a pivotal energy vector. However, their activity remains moderate, and ...descriptors to design improved systems are lacking. This work applies flame spray pyrolysis (FSP), a one‐step and scalable method, to synthesize a series of ZnZrO
x
catalysts, and systematically compares them to coprecipitated (CP) analogs to establish deeper synthesis–structure–performance relationships. FSP systems (up to 5 mol%) generally display a threefold higher methanol productivity compared to their CP counterparts. In‐depth characterization and theoretical simulations show that, unlike CP, FSP maximizes the surface area and formation of atomically dispersed Zn
2+
sites incorporated in lattice positions within the ZrO
2
surface, which is key to improving performance. Analysis by in situ electron paramagnetic resonance (EPR) spectroscopy reveals that the specific architecture of the flame‐made catalyst markedly fosters the generation of oxygen vacancies. Together with surrounding Zn and Zr‐O atoms, the oxygen vacancies create active ensembles that favor methanol formation through the formate path while suppressing undesired CO production, as confirmed by kinetic modeling. This study elucidates the nature of active sites and their working mechanism, pushing forward ZnZrO
x
‐catalyzed methanol synthesis by providing a new benchmark for this cost‐effective and earth‐abundant catalyst family.
Flame Spray Pyrolysis
In article number 2103707, Núria López, Javier Pérez‐Ramírez and co‐workers apply flame spray pyrolysis as a standardized synthesis method to investigate promotional effects of ...nine transition metals in In2O3‐catalyzed CO2 hydrogenation to methanol, revealing that catalyst architecture (single atoms, clusters, and nanoparticles) and corresponding reactivity are dictated by the nature of the promoter.
Abstract Background We hypothesized that the clinical course of venous thromboembolism in patients with active cancer may differ according to the specificities of primary tumor site. Aim and Methods ...We used data from RIETE (international registry of patients with venous thromboembolism) to compare the clinical venous thromboembolism-related outcomes during the course of anticoagulation in patients with with one of the 4 more frequent cancer (breast, prostate, colorectal or lung cancer). Results As of September 2014, 3947 cancer patients were recruited, of whom 938 had breast, 629 prostate, 1189 colorectal and 1191 lung cancer. Overall, 55% had metastatic disease (42%, 36%, 53%, and 72%, respectively). During the course of anticoagulant therapy (mean duration, 139 days), the rate of thromboembolic recurrences was similar to the rate of major bleeding in patients with breast (5.6 95%CI: 3.8-8.1 vs. 4.1 95%CI: 2.7-5.9 events per 100 patient-years) or colorectal cancer (10 95%CI: 7.6-13 vs. 12 95%CI: 9.4-15 per 100 patient-years). In contrast, in patients with prostate cancer, the rate of venous thromboembolic recurrences was half the rate of major bleeding (6.9 95%CI: 4.4-10 vs. 13 95%CI: 9.2-17 events per 100 patient-years) whereas in those with lung cancer, the rate of thromboembolic recurrences was two-fold higher than the rate of major bleeding (27 95%CI: 22-23 vs. 11 95%CI: 8.6-15 per 100 patient-years). Conclusions Significant differences in the clinical profile of venous thromboembolic related outcomes were observed according to the site of cancer. These findings suggest the development of cancer-specific anticoagulant strategies as an area for further research.
Abstract
A plethora of metal promoters have been applied to enhance the performance of In
2
O
3
in CO
2
hydrogenation to methanol, a prospective energy carrier. However, the lack of systematic ...catalyst preparation and evaluation precludes a direct comparison of their speciation and promotional effects, and consequently, the design of an optimal system. Herein, flame spray pyrolysis (FSP) is employed as a standardized synthesis method to introduce nine metal promoters (0.5 wt.%) into In
2
O
3
. Methanol productivity generally increased on
M
‐In
2
O
3
with selectivity following Pd ≈ Pt > Rh ≈ Ru ≈ Ir > Ni ≈ Co > Ag ≈ In
2
O
3
> Au. In‐depth characterization, kinetic analyses, and theoretical calculations reveal a range of metal‐dependent speciation which dictate catalyst architecture and degree of promotion. Atomically‐dispersed promoters (Pd, Pt, Rh, Ru, and Ir) grant the highest improvement in performance, particularly Pd and Pt, which markedly promote hydrogen activation while hindering undesired CO formation. In contrast, metals in clustered (Ni and Co) and nanoparticle (Ag and Au) forms display moderate and no promotion, respectively. This study provides an atomic‐level understanding of In
2
O
3
promotion based on a unified protocol, and highlights the potential of FSP to engineer complex catalytic systems toward more efficient energy transformations.
PDF