Amine Coordinated Electron-Rich Palladium Nanoparticles for Electrochemical Hydrogenation of Benzaldehyde

Electrocatalytic hydrogenation (ECH) is a burgeoning strategy for the sustainable utilization of hydrogen. However, how to effectively suppress the competitive hydrogen evolution reaction (HER) is a big challenge to ECH catalysis. In this study, amine (NH₂ R)-coordinated Pd nanoparticles loaded on carbon felt (Pd@CF) as a catalyst is successfully synthesized by a one-step solvothermal reduction method using oleylamine as the reducing agent. An exceptional ECH reactivity on benzaldehyde is achieved on the optimal Pd@CF catalyst in terms of a high conversion (89.7%) and selectivity toward benzyl alcohol (89.8%) at −0.4 V in 60 min. Notably, the Faradaic efficiency for producing benzyl alcohol is up to 90.2%, much higher than that catalyzed by Pd@CF-without N-group (41.1%) and thecommercial Pd/C (20.9%). The excellent ECH performance of Pd@CF can be attributed to the enriched electrons on Pd surface resulted from the introduction of NH₂ R groups, which strengthens both the adsorption of benzaldehyde and the adsorbed hydrogen (H_ads) on Pd, preventing the combination of H_ads to form H₂, that is, inhibiting the HER. This study gives a new insight into design principles of highly efficient electrocatalysts for the hydrogenation of unsaturated aldehydes molecules.     

Ultrafast Switchable Passive Radiative Cooling Smart Windows with Synergistic Optical Modulation

Switchable passive radiative cooling (PRC) smart windows can modulate sunlight transmission and spontaneously emit heat to outer space through atmospheric transparent window, presenting great potential in building energy conservation. However, realizing stable and on-demand control of the cooling efficiency for PRC materials is still challenging. Herein, an electro-controlled polymer-dispersed liquid crystal (PDLC) smart window showing PRC property is designed and prepared by adding mid-infrared emitting reactive monomers into the conventional PDLC matrix. It is found that not only the electro-optical properties but also the PRC efficiency of PRC PDLC film are tunable by regulating the content of the mid-infrared emitting components, film thickness, and micromorphology. This advanced PRC PDLC material achieves a near/sub-ambient temperature when the solar irradiance is below 400 W m⁻² and can dynamically manage daytime cooling efficiency. Importantly, its PRC efficiency is capable of being tuned in an on-demand and ultrafast millisecond-scale way, whose controllable transparency enables multistage heat regulation. This study is hoped to provide new inspiration in the preparation of advanced optical devices and energy-efficient equipment.     

A 2.20 eV Bandgap Polymer Donor for Efficient Colorful Semitransparent Organic Solar Cells

Semitransparent organic solar cells (ST-OSCs) have attracted increasing attention due to their promising prospect in building-integrated photovoltaics. Generally, efficient ST-OSCs with good average visible transmittance (AVT) can be realized by developing active layer materials with light absorption far from the visible light range. Herein, the development of ultrawide bandgap polymer donors with near-ultraviolet absorption, paired with near-infrared acceptors, is proposed to achieve high-performance ST-OSCs. The key points for the design of ultrawide bandgap polymers include constructing donor–donor type conjugated skeleton, suppressing the quinoidal resonance effect, and minimizing the twist of conjugated skeleton via noncovalent conformational locks. As a proof of concept, a polymer named PBOF with an optical bandgap of 2.20 eV is synthesized, which exhibited largely reduced overlap with the human eye photopic response spectrum and afforded a power conversion efficiency (PCE) of 16.40% in opaque device. As a result, ST-OSCs with a PCE over 10% and an AVT over 30% are achieved without optical modulation. Moreover, colorful ST-OSCs with visual aesthetics can be achieved by tuning the donor/acceptor weight ratio in active layer benefiting from the ultrawide bandgap nature of PBOF. This study demonstrates the great potential of ultrawide bandgap polymers for efficient colorful ST-OSCs.     

Design techniques for voltage-to-time converters with nonlinearity emphasis

This paper provides an in-depth treatment of voltage-to-time converters (VTCs) for time-based signal processing with a nonlinearity emphasis. The need for VTCs in deployment of time-based techniques for high-speed or high-resolution analog-to-digital converters is investigated. It is followed with the classification of VTCs. A detailed treatment of the principle, topology, operation, and design consideration of variable-slope (VS) and constant-slope (CS) VTCs is provided. The nonlinearity of VS-VTCs and that of CS-VTCs are analyzed in detail analytically. It is shown that VS-VTCs is inherently nonlinear while CS-VTCs is intrinsically linear. Factors contributing to the nonlinearity of these VTCs are investigated. VS-VTCs and CS-VTCs studied are designed in TSMC 130 nm 1.2 V CMOS and analyzed using Spectre from Cadence Design Systems with BSIM3.3 device models. A good agreement between simulation and analytical results is obtained. The average gain of the VS-VTC is 4.4 times that of the CS-VTC. The 2nd and 3rd harmonics of the CS-VTC are significantly smaller as compared with those of the VS-VTC at the price of more power consumption.

     

Chaotic electronic scattering with He(+)

We investigate classical electronic collisions with a He(+) ion. Scattering functions, such as the scattering angle, collisional time, or energy of the outgoing electron, all exhibit an interesting hierarchial self-similar structure, which can be interpreted in terms of the indefinite number of electronic returns to the vicinity of the nucleus, encounters between electrons, and Keplerian excursions of electrons during the collisional processes. Based on this mechanism a binary coding is introduced to organize the dynamics of this three-body system and to provide an understanding of the self-similarity among generations of scale magnification, which yields escape rates that vary with the sectional cut into the parameter space. The self-similarity displayed within a single generation, on the other hand, can be simply tied to the periods of the two independent electronic excursions. The physical interpretation and the symbolic dynamics introduced here are generally useful for three-body collisional systems, including atomic, molecular, or stellar collisions.     

Dynamics of photodissociation of 3,3,3-d(3)-propene at 157 nm: site effect and hydrogen migration

In a preceding paper [Lee et al., J. Chem. Phys. 119, 827 (2003)], we measured the kinetic-energy distributions P(E(t)) and branching ratios of products from photolysis of propene at 157 nm using time-of-flight spectroscopy combined with photoionization. In the present work, hydrogen migration before fragmentation and a site effect on P(E(t)) and branching ratios were revealed from the photodissociation of CD(3)CHCH(2). Labeling of the methyl group with deuterium enabled us to differentiate between elimination of atomic and molecular hydrogen from the vinyl moiety and from the methyl moiety; the P(E(t)) and relative yields for the formation of H, D, H(2), HD, and D(2) were measured. Deuterium labeling allowed us to also differentiate the fragmentation after hydrogen transfer from that before hydrogen migration. The observation of isotopic variants of CD(3) and C(2)H(3) radicals in the C-C bond cleavage provides evidence for hydrogen transfer of propene because of site specificity. The fraction of fragmentation after hydrogen transfer is estimated to be 25%. The isotope-specific branching ratios for five dissociation pathways of CD(3)CHCH(2) were evaluated.     

Sol-gel derived carbon ceramic electrode containing methylene blue-intercalated α-zirconium phosphate micro particles

Methylene blue-intercalated alpha-zirconium phosphate (MBZrP) micro particles in deionized water were deposited onto the surface of graphite powder to prepare graphite powder-supported MBZrP, which was subsequently dispersed into methyltrimethoxysilane-derived gels to yield a conductive composite. The composite was used as electrode material to fabricate a surface-renewable, rigid, leak-free carbon ceramic composite electrode, bulk-modified with methylene blue (MB). In the configuration, alpha-zirconium phosphate was employed as a solid host for MB, which acted as a catalyst. Graphite powder ensured conductivity by percolation, the silicate provided a rigid porous backbone and the methyl groups endowed hydrophobicity and thus limited the wetting section of the modified electrode. Peak currents of the MBZrP-modified electrode were surface-confined at low scan rates but diffusion-controlled at high scan rates. Square-wave voltammetric study revealed that MBZrP immobilized in carbon ceramic matrix presented a two-electron, three-proton redox process in acidic aqueous solution with pH ranged from 0.44 to 2.94. In addition, the chemically modified electrode showed an electrocatalytic activity toward nitrite reduction at +0.15 V ( vs. Ag/AgCl) in acidic aqueous solution (pH=0.44). The linear range and detection limit are 1x10(-6)-4x10(-3) mol x L(-1) and 1.5x10(-7) mol x L(-1), respectively.     

The Reaction of Triplet State Benzophenone with Acetylacetone

Irradiation of benzophenone in acetic acid containing acetylacetone resulted in regiospecific addition to form cis-2,2-dihpenyl-3-hydroxy-3-methyl-4-acetyloxetane and the rearrangement products therefrom. In the co-presence of copper ions, the regiospecificity is scrambled to give these products and a small amount of 1,1-diphenyl-1-buten-3-one, the secondary decomposition product of the other oxetane arising from the alternative orientation of the addition.