Size effect has been regularly utilized to tune the catalytic activity and selectivity of metal nanoparticles (NPs). Yet, there is a lack of understanding of the size effect in the electrocatalytic reduction of CO2, an important reaction that couples with intermittent renewable energy storage and carbon cycle utilization. We report here a prominent size-dependent activity/selectivity in the electrocatalytic reduction of CO2 over differently sized Pd NPs, ranging from 2.4 to 10.3 nm. The Faradaic efficiency for CO production varies from 5.8% at -0.89 V (vs reversible hydrogen electrode) over 10.3 nm NPs to 91.2% over 3.7 nm NPs, along with an 18.4-fold increase in current density. Based on the Gibbs free energy diagrams from density functional theory calculations, the adsorption of CO2 and the formation of key reaction intermediate COOH* are much easier on edge and corner sites than on terrace sites of Pd NPs. In contrast, the formation of H* for competitive hydrogen evolution reaction is similar on all three sites. A volcano-like curve of the turnover frequency for CO production within the size range suggests that CO2 adsorption, COOH* formation, and CO* removal during CO2 reduction can be tuned by varying the size of Pd NPs due to the changing ratio of corner, edge, and terrace sites.
Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.
Monodisperse poly(styrene-b-semifluorinated side chain) block copolymers were synthesized by anionic polymerization of poly(styrene-b-1,2/3,4-isoprene) followed by the corresponding polymer analogous reactions. By controlling the block copolymer composition and the relative lengths of the fluorocarbon and hydrocarbon units in the side group, the effect of chemical structure on surface properties and the influence of liquid crystalline structure of the semifluorinated side chain on the surface behavior were evaluated. The composition of side groups does not greatly affect the as-prepared sample surface tension, but influences instead the transition temperatures of the room temperature liquid crystal phase. It was observed that the shorter fluorocarbon units (six −CF2− units) form a smectic A phase at room temperature. The critical surface tension of the SA phase is 10.8 mN/m, and the polymer surface undergoes significant reconstruction when immersed in water. However, when the fluorocarbon side chain contains more than eight −CF2− units, the resulting surface possesses a lower critical surface tension (ca. 8 mN/m) and exhibits negligible surface reconstruction. We believe the stability results from the highly ordered packing of the room temperature smectic B phase. This mesophase resists the reconstruction of the surface, since to do so would require loss of the enthalpies of transition. The estimated activation energy to destroy the smectic B phase is about 3−10 times higher than that of smectic A phase. This phase forms a uniform, hexagonally packed −CF3 terminated surface with a low critical surface tension similar to that of fluorocarbon-based Langmuir−Blodgett films. The self-assembly of these liquid crystalline block copolymers at both the molecular and microstructural level provides a valuable approach to creating stable, low surface energy materials.
Lithium-sulfur batteries show fascinating potential for advanced energy storage systems due to their high specific capacity, low-cost, and environmental benignity. However, the shuttle effect and the uncontrollable deposition of lithium sulfide species result in poor cycling performance and low Coulombic efficiency. Despite the recent success in trapping soluble polysulfides via porous matrix and chemical binding, the important mechanism of such controllable deposition of sulfur species has not been well understood. Herein, we discovered that conductive Magnéli phase Ti4O7 is highly effective matrix to bind with sulfur species. Compared with the TiO2-S, the Ti4O7-S cathodes exhibit higher reversible capacity and improved cycling performance. It delivers high specific capacities at various C-rates (1342, 1044, and 623 mAh g(-1) at 0.02, 0.1, and 0.5 C, respectively) and remarkable capacity retention of 99% (100 cycles at 0.1 C). The superior properties of Ti4O7-S are attributed to the strong adsorption of sulfur species on the low-coordinated Ti sites of Ti4O7 as revealed by density functional theory calculations and confirmed through experimental characterizations. Our study demonstrates the importance of surface coordination environment for strongly influencing the S-species binding. These findings can be also applicable to numerous other metal oxide materials.
Current approaches for efficient C À H bond activation are usually mediated by heterogeneous  or homogeneous  catalysts. The basis is the employment of transition metals or organometallic centers, which is pivotal for the successful attack on the targeted C À H bonds.  However, we have reported that it is feasible to use carbon-based nanomaterials to activate short-chain alkanes in catalytic dehydrogenation reactions  although relatively high reaction temperatures are required. It is of particular interest to know whether it is possible to activate CÀH bonds to get high value-added products at a moderate reaction temperatures by using cheap metal-free catalysts. To this end, an elegant approach using metal-or boron-doped carbon nitrides as catalysts  has been developed for the selective oxidation of allylic and benzylic hydrocarbons in organic solvents with moderate conversion. Attempts to achieve higher activity also include the application of N-alkoxysulfonyloxaziridines for the activation of C(sp 3 ) À H bonds,  although a complicated catalytic system for efficient reaction circulation was required.Layered carbon, that is, highly exfoliated graphitic structures containing one or a few graphene layers,  has an unconventional electronic structure,  which was speculated to have a high chemical reactivity.  Indeed, researchers observed that layered carbon can catalyze hydrogenation,  ring-opening polymerization,  and CÀH oxidation reaction,  and that it could serve as a support for metal oxide catalysts.  Herein we describe nitrogen-doped graphene materials that can activate the benzylic C À H bond with exceptionally high activity. The nitrogen atoms introduced are preferentially bound at graphitic sites in the carbon framework. This induces high charge and spin density at the adjacent ortho carbon, which promotes the formation of reactive oxygen species and the materials display exceptional catalytic activity even at room temperature.Firstly, we examined the oxidation of ethylbenzene in aqueous phase with tert-butyl hydroperoxide (TBHP) as the oxidant and without using catalyst. However, no obvious activity was observed by GC after a reaction time of 24 h (Table 1, entry 1). Then we used a graphene sample prepared by the arc-discharge method (referred to as Arc-C)  as the catalyst for this reaction. Surprisingly, Arc-C activated ethylbenzene at 353 K to generate acetophenone in 20.7 % yield (Table 1, entry 2). As Arc-C had been prepared by a directcurrent arc-discharge method with a pure graphite rod as the electrode in an NH 3 /He atmosphere, besides trace nitrogen (0.7 %), no element other than carbon was detected by elemental analysis (EA) (oxygen cannot be detected by this method). The full X-ray photoelectron spectrum showed a C content of 97.9 % and low amounts of nitrogen and oxygen of 0.9 % and 1.1 %, respectively. This promising observation suggests that it is layered carbon material itself that catalyzed the oxyfunctionalization of the hydrocarbon. As Arc-C...
We investigate the relationship between the linewidths of broad Mg II λ2800 and Hβ in active galactic nuclei (AGNs) to refine them as tools to estimate black hole (BH) masses. We perform a detailed spectral analysis of a large sample of AGNs at intermediate redshifts selected from the Sloan Digital Sky Survey, along with a smaller sample of archival ultraviolet spectra for nearby sources monitored with reverberation mapping (RM). Careful attention is devoted to accurate spectral decomposition, especially in the treatment of narrow-line blending and Fe II contamination. We show that, contrary to popular belief, the velocity width of Mg II tends to be smaller than that of Hβ, suggesting that the two species are not cospatial in the broad-line region. Using these findings and recently updated BH mass measurements from RM, we present a new calibration of the empirical prescriptions for estimating virial BH masses for AGNs using the broad Mg II and Hβ lines. We show that the BH masses derived from our new formalisms show subtle but important differences compared to some of the mass estimators currently used in the literature.
The synthesis and characterization of a family of well-defined liquid crystal−coil (LC−coil) diblock copolymers have been carried out. The block copolymers in this study have been designed to have nearly identical molecular weight azobenzene-containing LC blocks in order to eliminate possible variations in LC behavior caused by the differences in the LC block molecular weight. Quantitative hydroboration chemistry was used to convert the pendent double bonds of an isoprene block to hydroxyl groups to which the mesogenic groups were attached via acid chloride coupling. The LC homopolymer and the block copolymers (LC volume fraction from f LC = 0.82 to f LC = 0.20) all exhibited smectic mesophases with similar clearing transition temperatures. The clearing transition enthalpies strongly depend on the block composition ratio and decrease as the LC block volume fraction decreases. Solvent-casting of a lamellar LC−coil copolymer (SICN5-66/60) resulted in an oriented bulk film in which both the axes of the mesogenic groups and the lamellar interfaces lie parallel to the film surfaces. A LC cylinder morphology was observed with a f LC = 0.22 LC-containing block (SICN5-176/55) using TEM and confirmed by SAXS measurements. This is the first observation with the LC block in a cylinder microdomain. Other morphologies (bicontinuous, LC sphere) were observed by TEM while retaining the smectic order in the LC microphase.
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