RESUMEN
Integrating single atoms and clusters into one system represents a novel strategy for achieving the desired catalytic performance. In comparison to single-atom catalysts, catalysts combining single atoms and clusters harness the advantages of both, thus displaying greater potential. Nevertheless, constructing single-atom-cluster systems remains challenging, and the fundamental mechanism for enhancing catalytic activity remains elusive. In this study, a directly confined preparation of a 3D hollow sea urchin-like carbon structure (MnSA/MnAC-SSCNR) is developed. Mn single atoms synergistically interact with Mn clusters, optimizing and reducing energy barriers in the reaction pathway, thus enhancing reaction kinetics. Consequently, in contrast to Mn single-atom catalysts (MnSA-SSCNR), MnSA/MnAC-SSCNR exhibits significantly improved oxygen reduction activity, with a half-wave potential (E1/2) of 0.90 V in 0.1 m KOH, surpassing that of MnSA-SSCNR and Pt/C. This work demonstrates a strategy of remote synergy between heterogeneous single atoms and clusters, which not only contributes to electrocatalytic reactions but also holds potential for reactions involving more complex products.
RESUMEN
Aqueous-phase oxygen evolution reaction (OER) is the bottleneck of water splitting. The formation of the O-O bond involves the generation of paramagnetic oxygen molecules from the diamagnetic hydroxides. The spin configurations might play an important role in aqueous-phase molecular electrocatalysis. However, spintronic electrocatalysis is almost an uncultivated land for the exploration of the oxygen molecular catalysis process. Herein, we present a novel magnetic FeIII site spin-splitting strategy, wherein the electronic structure and spin states of the FeIII sites are effectively induced and optimized by the Jahn-Teller effect of Cu2+. The theoretical calculations and operando attenuated total reflectance-infrared Fourier transform infrared (ATR FT-IR) reveal the facilitation for the O-O bond formation, which accelerates the production of O2 from OH- and improves the OER activity. The Cu1-Ni6Fe2-LDH catalyst exhibits a low overpotential of 210 mV at 10 mA cm-2 and a low Tafel slope (33.7 mV dec-1), better than those of the initial Cu0-Ni6Fe2-LDHs (278 mV, 101.6 mV dec-1). With the Cu2+ regulation, we have realized the transformation of NiFe-LDHs from ferrimagnets to ferromagnets and showcase that the OER performance of Cu-NiFe-LDHs significantly increases compared with that of NiFe-LDHs under the effect of a magnetic field for the first time. The magnetic-field-assisted Cu1-Ni6Fe2-LDHs provide an ultralow overpotential of 180 mV at 10 mA cm-2, which is currently one of the best OER performances. The combination of the magnetic field and spin configuration provides new principles for the development of high-performance catalysts and understandings of the catalytic mechanism from the spintronic level.
RESUMEN
Objective: This study evaluated the survival outcomes of young (<50 years) and elderly patients (>80 years) with high-risk prostate cancer (PCa) postradical local treatments. Materials and Methods: We identified <50 and >80-year-old patients with high-risk PCa between 2004 and 2015 in the Surveillance, Epidemiology, and End Results database. The patients aged 65 and 66 years were also identified as the control group. The propensity-score matching method was adopted to compare the young and elderly patients with the control group. Kaplan-Meier analysis and Cox regression were conducted to evaluate the PCa-specific survival (PCSS) and overall survival. Results: A total of 17726 patients were identified, and 3355 were under 50 years old, whereas 4798 of them were >80 years old. The young patient group (<50 years) had similar PCSS with the control group (65-66 years) in both the overall cohort (hazard ratio [HR]: 0.88, 95% confidence interval [CI] [0.73-1.06], P = 0.132) and matched cohort (HR: 0.96, 95% CI [0.74-1.24], P = 0.527). Young patients with both high-risk and very high-risk PCa after radical prostatectomy (RP) treatment had apparent longer mean cancer-specific survival time than those after external-beam radiotherapy (EBRT) and/or brachytherapy (BT) treatment (high-risk group: 153.38 ± 0.82 months vs. 149.72 ± 3.03 months; very high-risk group: 148.3 ± 1.84 months vs. 139.33 ± 3.25 months). For the elderly patients (>80 years), the PCSS outcomes were significantly worse than the control group (65-66 years) in both overall cohort (HR: 2.69, 95% CI [2.31-3.13], P < 0.001) and matched cohort (HR: 1.61, 95% CI [1.34-1.94], P < 0.001). Patients receiving RP treatment had similar PCSS outcomes with those receiving EBRT and/or BT in the high-risk PCa group (139.45 ± 9.98 months vs. 139.41 ± 1.84 months), and better PCSS in very high-risk PCa group (132.73 ± 13.56 months vs. 128.82 ± 3.43 months). Conclusion: The PCSS outcomes of young PCa patients (<0 years) were identical to those of the control group (65-66 years). RP had similar or better PCSS benefits than EBRT and/or BT in both young (<50 years) and elderly patients (>80 years).