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  1. Abstract

    Aqueous zinc-ion batteries, in terms of integration with high safety, environmental benignity, and low cost, have attracted much attention for powering electronic devices and storage systems. However, the interface instability issues at the Zn anode caused by detrimental side reactions such as dendrite growth, hydrogen evolution, and metal corrosion at the solid (anode)/liquid (electrolyte) interface impede their practical applications in the fields requiring long-term performance persistence. Despite the rapid progress in suppressing the side reactions at the materials interface, the mechanism of ion storage and dendrite formation in practical aqueous zinc-ion batteries with dual-cation aqueous electrolytes is still unclear. Herein, we design an interface material consisting of forest-like three-dimensional zinc-copper alloy with engineered surfaces to explore the Zn plating/stripping mode in dual-cation electrolytes. The three-dimensional nanostructured surface of zinc-copper alloy is demonstrated to be in favor of effectively regulating the reaction kinetics of Zn plating/stripping processes. The developed interface materials suppress the dendrite growth on the anode surface towards high-performance persistent aqueous zinc-ion batteries in the aqueous electrolytes containing single and dual cations. This work remarkably enhances the fundamental understanding of dual-cation intercalation chemistry in aqueous electrochemical systems and provides a guide for exploring high-performance aqueous zinc-ion batteries and beyond.

     
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  2. Abstract

    The stellar initial mass function (IMF) is a fundamental property in the measurement of stellar masses and galaxy star formation histories. In this work, we focus on the most massive galaxies in the nearby universelog(M/M)>11.2. We obtain high-quality Magellan/LDSS-3 long-slit spectroscopy with a wide wavelength coverage of 0.4–1.01μm for 41 early-type galaxies (ETGs) in the MASSIVE survey and derive high signal-to-noise spectra within an aperture ofRe/8. Using detailed stellar synthesis models, we constrain the elemental abundances and stellar IMF of each galaxy through full spectral modeling. All the ETGs in our sample have an IMF that is steeper than a Milky Way (Kroupa) IMF. The best-fit IMF mismatch parameter,αIMF= (M/L)/(M/L)MW, ranges from 1.1 to 3.1, with an average of 〈αIMF〉 = 1.84, suggesting that on average, the IMF is more bottom heavy than Salpeter. Comparing the estimated stellar masses with the dynamical masses, we find that most galaxies have stellar masses that are smaller than their dynamical masses within the 1σuncertainty. We complement our sample with lower-mass galaxies from the literature and confirm thatlog(αIMF)is positively correlated withlog(σ),log(M), andlog(Mdyn). From the combined sample, we show that the IMF in the centers of more massive ETGs is more bottom heavy. In addition, we find thatlog(αIMF)is positively correlated with both [Mg/Fe] and the estimated total metallicity [Z/H]. We find suggestive evidence that the effective stellar surface density ΣKroupamight be responsible for the variation ofαIMF. We conclude thatσ, [Mg/Fe], and [Z/H] are the primary drivers of the global stellar IMF variation.

     
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  3. Employing the strong metal-support interaction (SMSI) effect for promoting the catalyst's activity toward the oxygen reduction reaction (ORR) is promising due to the electronic structure optimization and high utilization efficiency of platinum group metal (PGM) catalysts. Metal oxides as alternative supports for PGMs facilitate intrinsic activity and improve durability as compared to conventional carbon supports. However, the restricted mass and electron transfer at the metal/support interface need to be addressed. Herein, to strengthen the interaction at the metal/support interfaces and improve the utilization efficiency of PGM, an ultralow loading of Pd was embedded in a surface-oxygenated PdNiMnO porous film. The Mn-doping was designed to promote surface oxygenation using a facile anodization process that created sufficiently exposed interfaces between Pd and the support, strengthening the SMSI effects at the Pd/oxygenated support interface for enhancing ORR performance. Furthermore, the Ni-containing oxygenated catalyst served as both the active component for the oxygen evolution reaction (OER) and the functional support for stabilizing Pd, making PdNiMnO a bifunctional catalyst for zinc–air flow batteries (ZAFB). As a proof-of-concept, the ZAFB (PdNiMnO) shows a maximal power density of 211.6 mW cm −2 and outstanding cycling stability for over 2000 h with a minimal voltage gap of 0.69 V at a current density of 10 mA cm −2 , superior to the state-of-the-art catalysts. 
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  4. Abstract

    Surface ligands play an important role in shape‐controlled growth and stabilization of colloidal nanocrystals. Their quick removal tends to cause structural deformation and/or aggregation to the nanocrystals. Herein, we demonstrate that the surface ligand based on poly(vinylpyrrolidone) (PVP) can be slowly removed from Pd nanosheets (NSs, 0.93±0.17 nm in thickness) by simply aging the colloidal suspension. The aged Pd NSs show well‐preserved morphology, together with significantly enhanced stability toward both e‐beam irradiation and electrocatalysis (e.g., ethanol oxidation). It is revealed that the slow desorption of PVP during aging forces the re‐exposed Pd atoms to reorganize, facilitating the surface to transform from being nearly perfect to defect‐rich. The resultant Pd NSs with abundant defects no longer rely on surface ligand to stabilize the atomic arrangement and thus show excellent structural and electrochemical stability. This work provides a facile and effective method to maintain the integrity of colloidal nanocrystals by slowly removing the surface ligand.

     
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  5. Abstract

    Surface ligands play an important role in shape‐controlled growth and stabilization of colloidal nanocrystals. Their quick removal tends to cause structural deformation and/or aggregation to the nanocrystals. Herein, we demonstrate that the surface ligand based on poly(vinylpyrrolidone) (PVP) can be slowly removed from Pd nanosheets (NSs, 0.93±0.17 nm in thickness) by simply aging the colloidal suspension. The aged Pd NSs show well‐preserved morphology, together with significantly enhanced stability toward both e‐beam irradiation and electrocatalysis (e.g., ethanol oxidation). It is revealed that the slow desorption of PVP during aging forces the re‐exposed Pd atoms to reorganize, facilitating the surface to transform from being nearly perfect to defect‐rich. The resultant Pd NSs with abundant defects no longer rely on surface ligand to stabilize the atomic arrangement and thus show excellent structural and electrochemical stability. This work provides a facile and effective method to maintain the integrity of colloidal nanocrystals by slowly removing the surface ligand.

     
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  6. null (Ed.)
    The alkaline hydrogen evolution reaction (A-HER) holds great promise for clean hydrogen fuel generation but its practical utilization is severely hindered by the sluggish kinetics for water dissociation in alkaline solutions. Traditional ways to improve the electrochemical kinetics for A-HER catalysts have been focusing on surface modification, which still can not meet the demanding requirements for practical water electrolysis because of catalyst surface deactivation. Herein, we report an interior modification strategy to significantly boost the A-HER performance. Specifically, a trace amount of Pt was doped in the interior Co 2 P (Pt–Co 2 P) to introduce a stronger dopant–host interaction than that of the surface-modified catalyst. Consequently, the local chemical state and electronic structure of the catalysts were adjusted to improve the electron mobility and reduce the energy barriers for hydrogen adsorption and H–H bond formation. As a proof-of-concept, the interior-modified Pt–Co 2 P shows a reduced onset potential at near-zero volts for the A-HER, low overpotentials of 2 mV and 58 mV to achieve 10 and 100 mA cm −2 , and excellent durability for long-term utilization. The interior-modified Pt–Co 2 P delivers superior A-HER performance to Pt/C and other state-of-the-art electrocatalysts. This work will open a new avenue for A-HER catalyst design. 
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  7. null (Ed.)
    Changes in the local atomic arrangement in a crystal caused by lattice-mismatch-induced strain can efficiently regulate the performance of electrocatalysts for zinc–air batteries (ZABs) in many manners, mainly due to modulated electronic structure configurations that affect the adsorption energies for oxygen-intermediates formed during oxygen reduction and evolution reactions (ORR and OER). However, the application of strain engineering in electrocatalysis has been limited by the strain relaxation caused by structural instability such as dissolution and destruction, leading to insufficient durability towards the ORR/OER. Herein, we propose a doping strategy to modulate the phase transition and formation of self-supported cobalt fluoride–sulfide (CoFS) nanoporous films using a low amount of copper (Cu) as a dopant. This well-defined Cu–CoFS heterostructure overcomes the obstacle of structural instability. Our study of the proposed Cu–CoFS also helps establish the structure–property relationship of strained electrocatalysts by unraveling the role of local strain in regulating the electronic structure of the catalyst. As a proof-of-concept, the Cu–CoFS electrocatalyst with doping-modulated strain exhibited superior onset potentials of 0.91 V and 1.49 V for the ORR and OER, respectively, surpassing commercial Pt/C@RuO 2 and benchmarking non-platinum group metal (non-PGM) catalysts. ZABs with the Cu–CoFS catalyst delivered excellent charge/discharge cycling performance with an extremely low voltage gap of 0.5 V at a current density of 10 mA cm −2 and successively 0.93 V at a high current density of 100 mA cm −2 and afforded an outstanding peak power density of 255 mW cm −2 . 
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  8. Abstract

    The development of solid‐state sodium‐ion batteries (SSSBs) heavily hinges on the development of an superionic Na+conductor (SSC) that features high conductivity, (electro)chemical stability, and deformability. The construction of heterogeneous structures offers a promising approach to comprehensively enhancing these properties in a way that differs from traditional structural optimization. Here, this work exploits the structural variance between high‐ and low‐coordination halide frameworks to develop a new class of halide heterogeneous structure electrolytes (HSEs). The halide HSEs incorporating a UCl3‐type high‐coordination framework and amorphous low‐coordination phase achieves the highest Na+conductivity (2.7 mS cm−1at room temperature, RT) among halide SSCs so far. By discerning the individual contribution of the crystalline bulk, amorphous region, and interface, this work unravels the synergistic ion conduction within halide HSEs and provides a comprehensive explanation of the amorphization effect. More importantly, the excellent deformability, high‐voltage stability, and expandability of HSEs enable effective SSSB integration. Using a cold‐pressed cathode electrode composite of uncoated Na0.85Mn0.5Ni0.4Fe0.1O2and HSEs, the SSSBs present stable cycle performance with a capacity retention of 91.0% after 100 cycles at 0.2 C.

     
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