RESUMO
Despite stunning progress in single-atom catalysis (SAC), it remains a grand challenge to yield a high loading of single atoms (SAs) anchored on substrates. Herein, we report a one-step laser-planting strategy to craft SAs of interest under an atmospheric temperature and pressure on various substrates including carbon, metals, and oxides. Laser pulses render concurrent creation of defects on the substrate and decomposition of precursors into monolithic metal SAs, which are immobilized on the as-produced defects via electronic interactions. Laser planting enables a high defect density, leading to a record-high loading of SAs of 41.8 wt %. Our strategy can also synthesize high-entropy SAs (HESAs) with the coexistence of multiple metal SAs, regardless of their distinct characteristics. An integrated experimental and theoretical study reveals that superior catalytic activity can be achieved when the distribution of metal atom content in HESAs resembles the distribution of their catalytic performance in a volcano plot of electrocatalysis. The noble-metal mass activity for a hydrogen evolution reaction within HESAs is 11-fold over that of commercial Pt/C. The laser-planting strategy is robust, opening up a simple and general route to attaining an array of low-cost, high-density SAs on diverse substrates under ambient conditions for electrochemical energy conversion.
RESUMO
Developing active and cost-effective bifunctional electrocatalysts for overall water splitting is challenging but mandatory for renewable energy technologies. We report a high-entropy alloy (HEA) of PtIrCuNiCr as a bifunctional electrocatalyst for overall water splitting, which shows a low overpotential of ca. 190 mV at the current density of 10 mA cm-2. Compared with pure metals, HEAs exhibit remarkable surface strain due to severe lattice distortion in their crystal structures. Theoretical calculations reveal that the strain can regulate the binding energy of intermediates on catalysts by adjusting the metal-metal bonding energy. It pushes the HEA toward the top of volcano plots to achieve superior electrocatalytic activity for both hydrogen and oxygen evolution reactions. The strain effect of HEAs on electrocatalysis can be well engineered by tuning the catalyst radius or configurational entropy. This work renders a systematic strain regulation strategy for designing a high-performance HEA catalyst for overall water splitting.
RESUMO
Heparanase (HPSE) plays a critical role in tumor metastasis and vascularization. In addition, the human HPSE promoter has been cloned and characterized. However, the activity and specificity of the HPSE promoter in tumor cells remains unclear. The core fragment of the HPSE promoter was amplified and cloned into the multiple cloning site of the pEGFP-1 vector. The recombinant plasmid pEGFP-Hp was transfected into human umbilical vein endothelial cells (ECV304) and human hepatoma carcinoma (HepG2), laryngocarcinoma (Hep2) and chronic myelogenous leukemia (K562) cell lines. The vectors pEGFP-1 and pEGFPN1 were used as negative and positive controls, respectively. The activity and expression of green fluorescent protein (GFP) were analyzed. Results showed that the sequence of the amplified HPSE promoter was in agreement with the GenBank data. The recombinant plasmid pEGFP-Hp was consistent with the expected result. No GFP expression was observed in the transfected cells in the pEGFP-1 group, but a high expression was observed in the pEGFP-N1 group. As regards the pEGFP-Hp group, less fluorescence was revealed in ECV cells with a relatively high fluorescence in tumor cells. The average transfection efficiencies of pEGFP-Hp in the ECV304, HepG2, Hep2 and K562 cell lines were 3.9, 21.3, 10.8 and 6.5%, respectively, while those of pEGFP-Nl were 17.1, 24.0, 14.0 and 11.0%, respectively. The HPSE gene promoter drives the expression of downstream genes in a eukaryotic vector, specifically in tumor cell lines, but its activity is relatively weak.
